Low environmental impact pesticide made from &#34;gras&#34; ingredients for use against coqui frogs and other species

ABSTRACT

The current invention involves compositions and methods for killing various soft-bodied animals of interest with a low pH adjusted pesticide. The method involves contacting the soft-bodied animal of interest with the low pH adjusted pesticide, wherein the pesticide is a propionic acid composition, a citric acid composition, an Acidic Calcium Sulfate composition, or combination thereof. The pesticide has a lethal effect on Coqui frogs, but is less phytotoxic than higher concentration pesticides. The method includes spraying any of the pH adjusted pesticides thoroughly an area inhabited by the soft-bodied animals of interest, including any typical hiding places. On a large scale, the method contemplates filling various types of industrial spraying equipment with the pesticide and saturating entire pest inhabited areas.

RELATED APPLICATIONS

This application claims priority to U.S. Non-provisional patentapplication Ser. No. 12/763,392, which claims priority from U.S.Provisional Patent Application Ser. No. 61/170,987 (now abandoned)titled “New Pesticide use for Propionic acid and/or its salts with orwithout the addition of ACS or ACS-P,” filed on Apr. 20, 2009, havingDavid Paul Davis, listed as inventor, the entire content of which ishereby incorporated by reference.

FEDERALLY SPONSORED RESEARCH

No federal funds were used in the development of the present invention.

JOINT RESEARCH AGREEMENTS

Not Applicable.

SEQUENCE LISTING

Not Applicable.

BACKGROUND

One aspect of this invention is an environmentally friendly, lowphyotoxic acidic aqueous pesticide composition and a method for killinga soft-bodied animal (e.g. a Coqui frog; a Coqui frog egg; a tree frog,a cane toad, a slug, a nettle, a caterpillar, a nematode, an aphid, aspider mite, fruit fly larva, a varro mite and other soft bodied insectsthat are usually regarded as pests, or a combination thereof). Morespecifically, the acidic aqueous pesticide composition comprises: a lowconcentration of organic acid solution (less than 25%) and having a lowpH (below about pH 3). The active ingredient in the pesticidecomposition can be selected from acidic calcium sulfate (ACS), propionicacid, citric acid, or various functional equivalents including salts andesters, as described herein. The acidic aqueous pesticide composition ofcan further be formulated to comprise a sulfuric acid solution having aconcentration below 10% (w/v) as a percentage of the aqueous pesticidecomposition. Additionally, the aqueous pesticide composition may furthercomprise a surfactant for the surface area of the aqueous pesticidecomposition on the soft bodied animal of interest wherein the surfactantis selected from: an ionic-, anionic-, zwitterionic-surfactant, orcombination thereof.

Another aspect of the current invention is a method of killing asoft-bodied animal of interest with an acidic pesticide composition, themethod comprising the steps of: locating the soft-bodied animal orlocating an area where the soft-bodied animal resides; contacting thesoft-bodied animal with one of the acidic pesticide compositionsdescribed herein. About 1 ml of this composition coming in contact withCoqui Frogs is lethal in less than about 15 minutes. This acidicpesticide composition represents a low environmental impact pesticidemade from all GRAS ingredients also used in food processing and whichare low in phytotoxicity.

The Coqui Frog:

Hawaii's lush vegetation, warm temperatures and high humidity not onlywelcome human visitors but also indiscriminately provide a tropicalparadise for the over 1,000 non-native plants, vertebrates, andinvertebrates that have been accidentally introduced over the past 65years. Some non-native species have become established at the expense ofnative species, competing for habitat and nutrient sources.

The Coqui frog, Eleutherodactylus coqui, was accidentally introducedinto Hawaii from Puerto Rico in about 1988. Aside from being a majornoise nuisance, the frogs pose a threat to Hawaii's island ecosystem.Coqui frogs have a voracious appetite that puts Hawaii's unique insectsand spiders at risk directly. These frogs also compete with endemicbirds and other native fauna that rely on insects for food. The frogsare quite adaptable to the different ecological zones and elevations inthe state, which is demonstrated by populations being found from sealevel to 4,000 feet elevations. Scientists are also concerned that anestablished coqui frog population may serve as a readily available foodsource if (or when) brown tree snakes are accidentally introduced inHawaii.

Coqui frogs belong to a genus of frogs that do not have a tadpole stageand therefore do not require a body of water to reproduce. Instead, thefemale lays the eggs on damp moss or leaf litter, or inside a rolled orfolded leaf, and the eggs are brooded by the male, who keeps them moistuntil they hatch.

At first, the eggs look white to off-white and opaque, about the size oflarge tapioca pearls. As they mature, the eggs enlarge, darken andbecome transparent, resembling papaya seeds, with the frog embryovisible inside. When the tiny froglets hatch in 14-17 days, they areabout 5 mm long.

In its native Puerto Rico, the female coqui frog usually lays a clusteror clutch of 34-75 eggs four to six times a year. Under laboratoryconditions in Hawaii, mating pairs can produce a clutch every 2½ weekswithout loss of fertility, which results in about 26 clutches per year,or more than 1,400 eggs per female per year. It takes about 8 months forfroglets to mature, and adult coqui frogs may live as long as 4-6 years.

Coqui populations have exploded in Hawaii over the last 15 years frompresumably a single infestation to over 200 infestations on the BigIsland alone. These frogs are also present on Maui (e.g. 40 or moreinfestations), O'ahu (5 sites) and most recently on Kaua'i (1 site,which was the subject of an eradication effort with citric acid). Intheir native Puerto Rico, a 20×20 m plot averages about 40reproductively mature adults (note: this number excludes juveniles). Incontrast, a 20×20 m plot on the big island contains >200 reproductivelymature adults. One reason for the population explosion is believed to bethe lack of natural predators (e.g. owls, snakes, tarantulas, scorpions)in Hawaii.

Respiration and Circulation in Frog Skin.

Although not wanting to be bound by theory, many of the methodsdescribed below take advantage of the skin of a frog being permeable tooxygen and carbon dioxide, as well as to water. Briefly, there are anumber of blood vessels near the surface of the skin. When a frog isunderwater, oxygen is transmitted through the skin directly into thebloodstream. On land, adult frogs can use their lungs to breathe, butthe chest muscles are not involved in respiration, and there are no ribsor diaphragm to support breathing. Frogs breathe by taking air inthrough the nostrils (which often have valves which close when the frogis submerged), causing the throat to puff out, then compressing thefloor of the mouth, which forces the air into the lungs. In August 2007an aquatic frog named Barbourula kalimantanensis was discovered in aremote part of Indonesia. The Bornean Flat-headed Frog (B.kalimantanensis) is the first species of frog known to science withoutlungs.

Frogs are known for their three-chambered heart, which they share withall tetrapods except birds, crocodilians and mammals. In thethree-chambered heart, oxygenated blood from the lungs and de-oxygenatedblood from the respiring tissues enter by separate atria, and aredirected via a spiral valve to the appropriate vessel—aorta foroxygenated blood and pulmonary artery for deoxygenated blood. Thisspecial structure is believed to be essential to keeping the mixing ofthe two types of blood to a minimum, which enables frogs to have highermetabolic rates, and to be more active than otherwise.

Some species of frog have remarkable adaptations that allow them tosurvive in oxygen deficient water. The lake titicaca frog (Telmatobiusculeus) is one such species and to survive in the poorly oxygenatedwaters of Lake Titicaca it has incredibly wrinkly skin that increasesits surface area of the skin to enhance gas exchange. This frog willalso do ‘push-ups’ on the lakebed to increase the flow of water aroundits body.

The Coqui frog has demonstrated its ability to quickly adapt to Hawaii'secosystem by an unprecedented population explosion that can reach eightto ten thousand frogs per square acre. Such a mega-group of frogs isestimated to eat about 47,500 insects per night. The absence of naturalpredators and its noisy mating behavior have made the Coqui frog thetarget of government and community eradication efforts. There are manydifferent methods currently used to control and eradicate the Coqui frogin Hawaii. Many of the eradication methods take advantage of the frogsability to breath through its skin. Some methods are described below,however, one of ordinary skill in the art will realize that the methodsof population control and/or eradication described herein are by nomeans all-inclusive.

Methods of Pest Population Control

The primary control methods include but are not limited to chemicalsprays, hot water sprays, hand capture and trapping, and environmentalmanagement. For lack of an acceptable and affordable commerciallyavailable pesticide, there are many environmentally hazardous substancesthat are being applied to infested areas by desperate residents seekingrelief form the noisy calling of the Coqui frog. Environmentalmanagement is preferred by those who are against the application ofchemicals and who are willing to clear away the vegetation andunderbrush in which the Coqui frog hides during the day and may lay itseggs. Although labor intensive and in some cases detrimental to thehorticultural diversity and appeal of the landscape, environmentalmanagement can be very effective and is especially useful in developingfrog free zones around commercial nurseries and public buildings. Ifeffective protocols are used in commercial nurseries to assuretransported plants are free from Coqui frogs, infestations of thisspecies to different parts of the island will continue.

Hand Capture.

The Hawaii Department of Agriculture personnel have devised a toolconsisting of a length of plastic tubing (e.g. fluorescent light tubeprotective sheath that is sold at hardware stores in 8-ft lengths) cutat an angle, with a plastic bag taped over one end. Place the open endof the tube over the frog, and the frog will invariably hop into thetube and can be tipped into the bag. Once the frogs have been captured,freezing can effectively euthanize them. One of the problems with thecapture approach is the amount of time required to capture and euthanizethe large numbers of frogs needed to reduce the infestation population.It is also very difficult for the average person to find and capture thefrogs, which are experts at calling from protected and hidden locations.Additionally, the capture and euthanize method does little to preventclutches of frog eggs from hatching shortly after the mature adults havebeen captured.

Another control method is to make a lure or trap out of PVC or bamboopipe. In order to accent the capture and euthanize methods, lures can beutilized to entice frogs into laying eggs in the lure wherein the frogsand eggs can be eradicated together. For example, Refugia Lures madefrom either bamboo or PVC pipe provides retreat and nesting site forCoqui frogs. These lures may comprise a ¾- to 1-inch inner diameter and8-10 inches in length of cylindrical bamboo or PVC pipe, which is closedon one end. A 1-inch drilled hole along the side of the tube, about 4inches from the closed end, serves as an entrance/exit for the frog.These lures can be preferred refuge sites or homes for the frogs whenthey are attached 3 to 5 ft above the ground on trees or stakes ininfested areas. Lure efficiency in tests at Lava Tree State MonumentPark has been estimated to be around 28% to 30%.

Although the frogs can freely come and go from the lures, they rarelytry to escape, especially when tending a clutch of eggs, and can beeasily captured. These devices are meant to LURE the frogs into usingeither the bamboo or PVC shelter instead of plants, trees or rock wallsto lay their eggs (like a birdhouse). Because the frogs are not“trapped”, the lures must be checked during the day at least every 2weeks because eggs hatch in about 14 days. Using the lure capturemethods, one of ordinary skill in the art can remove any adults thathave taken up residence, as well as any eggs. Captured frogs and eggsmay be destroyed by placing them in a zip lock bag or container andapplying any one of a number of treatments including, but not limitedto: filling the container with hot, soapy water (at least 113° F. for 3min.); freezing the frogs/eggs for at least 3 hours; or thoroughlyfrogs/eggs with chemicals known to kill frogs.

By destroying the egg clutch as well as the adult frog, one can reducethe population of Coqui frogs in the area, but will not eliminate anestablished population of Coqui frogs. Additionally, the lure methods donot work well in a densely vegetated area having ample natural nestingsites. However, one major problem with the lure, capture and euthanizemethod is assuring that the frogs and frog eggs are dead before disposalbecause this method has been shown to accidentally lead to froginfestations at dump sites. Moreover, the hand-capture and lure methodwill only serve to make minimal reductions in any frog population andare most useful as a backyard approach. Hot water sprays or rinses areprimarily used in nursery or commercial grower settings where theprocedure can be accomplished in a controlled setting.

Caffeine.

Caffeine is found in many plant species, where it acts as a naturalpesticide, with high caffeine levels being observed in seedlings thatare still developing foliages, but are lacking mechanical protection.Caffeine has been shown to paralyze and kill certain insects feedingupon the plant. High caffeine levels have also been found in thesurrounding soil of coffee bean seedlings. Therefore, it is understoodthat caffeine has a natural function as both a natural pesticide and aninhibitor of seed germination of other nearby coffee seedlings, thusgiving it a better chance of survival. Based on the natural pesticideproperties, the use of caffeine to control frogs has been utilized inthe past. However, one of the major drawbacks for the large scale use ofcaffeine to control frog populations is the high cost.

Pyrenone.

Pyrethrins are natural organic compounds that have potent insecticidalactivity. Pyrethrin I and pyrethrin II are structurally related esterswith a cyclopropane core. They differ by the oxidation state of onecarbon. They are viscous liquids that oxidize to become inactivated.They are non-persistent, being biodegradable, and break down on exposureto light or oxygen. The chemical structure of pyrethrins is the basisfor a variety of synthetic insecticides called pyrethroids such asbifenthrin, permethrin and cypermethrin. Pyrenone, a pyrethrin (BayerAG), was tested on Coqui frog eggs. Egg clusters or clutches (at least 4days old) were cleared of dead or infertile eggs and dissected into twomasses; one half was treated and the other served as untreated control.A solution of Pyrenone (14 oz/100 gal) was sprayed over the egg masses,which were observed until hatching. Nearly 92% of the eggs that weretreated with Pyrenone hatched, compared to 97% among the untreated eggs.For eggs at the ages tested (4-7 days after being laid), Pyrenone doesnot seem to provide effective control.

Hydrated Lime.

In 2005 hydrated lime was approved for use against the Coqui as anemergency local use pesticide, however it was very hazardous to use andunder strict controls. The use permit of hydrated lime expired in 2008,and although the state of Hawaii is considering asking for renewal forcommercial growers only they are concerned about the environmentalhazard potential. Additionally, this method of eradicating frogs leavesan unaesthetic white coating on plants, clogs sprayers, and is notentirely effective.

Spray Citric Acid Solution.

Taking advantage of the frog's unique respiratory and circulatory systemin the skin, commercially available organic weak acids have been sprayedonto frog infested plants to kill Coqui frog-eggs, -juveniles, and-mature adults. Citric acid is a weak organic acid, and it is a naturalpreservative and is also used to add an acidic, or sour, taste to foodsand soft drinks. In biochemistry, it is important as an intermediate inthe citric acid cycle and therefore occurs in the metabolism ofvirtually all living things.

Citric acid is an exempt active ingredient per 40 CFR 152.25(g), andaccording to EPA for ingredients on List 4A, no consideration needs tobe given to its effect on non-target species and or ground water. Only afew other organic acids like propionic acid and its salts as mentionedbelow are on List 4B, and are similarly permitted with an exempt status.As such, citric acid can also be used as an environmentally benigncleaning agent. In fact, lemons and limes have particularly highconcentrations of the acid; it can constitute as much as 8% of the dryweight of these fruits (about 47 g/L in the juices). The concentrationsof citric acid in citrus fruits ranging from 0.005 mol/L for oranges andgrapefruits to 0.30 mol/L in lemons and limes. Because citric acid is acommon food additive and is considered safe for environmental use by theEPA, it has been used in efforts to control the Coqui frog population inHawaii. More specifically, citric acid (anhydrous, or dry powder) can beobtained in 50 lb bags or in repackaged 5 and 10 lb bags from chemicalor garden supply stores. Typically, the citric acid dry powder must bemixed with water to make a 16% (w/v) solution, which is about 1.3 lbcitric acid per 1 gallon of water. Similar 16% citric acid solutions arealso available in ready-to-use premixed solutions.

Unfortunately, frogs and frog eggs are only killed by direct contactwith the spray and not by its residue. For maximum effectiveness, citricacid spraying should be done following removal of dense shrubs and deadfoliage to increase contact with the frog. Additionally, the sprayshould be applied in the early evening after a drizzle or heavy rain,when frogs start to call, rather than during a dry period or droughtwhen frogs remain hidden and call less frequently. Moderate to heavyrain will dilute and wash away sprayed citric acid, so a user shouldconsult the weather forecast prior to spraying. It is also important toprovide thorough coverage of plants with the citric acid solution,including undersides of leaves where frogs may be hiding. Spray orhand-capture frogs agitated by the citric acid that may jump out of theplants before they can find another hiding place. Frogs that are notdirectly contacted during citric acid spraying may retreat and males mayrefrain from calling for a few days before re-emerging. The user shouldrepeatedly spray the citric acid solution every two-weeks (time it takesfor eggs to hatch) and monitor for calling males up to one year becauseit takes time for hatchlings to mature.

One of the major drawbacks of liberally spraying citric acid every twoweeks for eradication of frogs is the mild to severe damage caused tomany plants. Citric acid sprayed on stressed, young, or growing plantscan range from mild (e.g. leaf spotting or yellowing) to severe (e.g.death of the plant). To avoid damage to delicate plants or flowers, itis necessary to thoroughly rinse the treated plants with fresh water tocompletely remove citric acid residue about an hour after spraying.However, this may reduce the effectiveness of the frog eradicationtreatment. Phytotoxicity (chemical damage) of plants varies depending onexposure conditions. Pre-testing on a small section of a plant is alwaysrecommended. After spraying and/or rinsing, observe the section for afew days for discoloration before spraying a large number of plants orvaluable plants. A simple phytotoxicity observation of common plantsthree days after treatment with citric acid (25%) can be rated assevere, moderate or light. For example, citric acid treatments onstreptocarpus, calathea and eggplants have a severe phytotoxicityoutcome. More specifically, most if not all the leaves turned black;flowers and leaves became bleached and recovery was slow. The guavaplant, bromeliad, dendrobium orchid and leatherleaf fern have a moderatephytotoxicity rating with citric acid, wherein young leaves and newshoots burned; the outer edges of leaves burned and dropped; dark brownspots appeared where acid may have concentrated; and recovery of theplants were slow. However, in passion fruit and payaya, thephytotoxicity to citric acid was only slight, wherein the leaves werespotted white, or lesions formed on the trunk.

Superacids.

Because many frogs are able to absorb water and oxygen directly throughthe skin, especially around the pelvic area, citric acid has been usedfor this to kill frogs by disrupting respiration. Citric acid is not aformal pesticide and has the unwanted problem of being highlyphytotoxic, even at relatively low concentrations (−16%). Althoughhigher concentrations of organic acids are more effective killing agentsfor the Coqui frog, the higher concentrations of acid are also morephytotoxic to the surrounding environment. The present inventionutilizes a highly acidic metalated organic acid that can be used aloneor as an acidiluant, or pH adjuster for organic acids, wherein theresultant composition is more dilute and having a more acidic pH, whichis capable of eradicating a frog population in an infested area, with aminimal phytotoxic effect. These highly acidic metalated organic acidsare also know as superacids.

A superacid is an acid with acidity greater than that of 100% puresulfuric acid, which has a Hammett acidity function (H₀) of −12.Commercially available superacids include trifluoromethanesulfonic acid(CF₃SO₃H), also known as triflic acid, and fluorosulfonic acid(F_(S)O₃H), both of which are about a thousand times stronger (i.e. havemore negative H₀ values) than sulfuric acid. The strongest superacidsare prepared by the combination of two components, a strong Lewis acidand a strong Brønsted acid.

The subject of U.S. Pat. No. 6,881,424 titled, “Highly Acidic MetalatedOrganic Acid,” issued on Apr. 19, 2005, having Kemp et al., listed asinventors (“the Kemp '424 patent”), describes the production of some ofthese types of Acidic Calcium Sulfate (ACS) acids, the entire referenceis hereby incorporated by reference. More specifically, the Kemp '424patent teaches a highly acidic metalated organic acid composition andits preparation. The acidic composition can be prepared by mixing amonovalent or polyvalent cation and an organic acid in the presence of astrong oxyacid, wherein the resultant acidic composition is lesscorrosive to a ferrous metal than a solution of a mineral acid havingthe same acidic pH value as that of the acidic composition, and where inthe acid composition is more biocidal than a mixture of the organic acidand a metal salt of the organic acid which mixture has the same acidnormality value as that of the acidic composition. The acidiccomposition can be prepared by mixing at least one regenerating acid, atleast one metal base, and at least one organic acid, wherein the amountof the regenerating acid is in excess of the equivalent amount of themetal base.

Additionally, the subject of U.S. Pat. No. 7,323,436 titled, “Adducthaving an acidic solution of sparingly-soluble group IIA complexes,”issued on Jan. 29, 2008 and having Kemp et al., listed as inventors(“the Kemp '436 patent”), describes an adduct having an acidic solutionof sparingly-soluble Group IIA complexes. More specifically, the Kemp'436 patent teaches an adduct having an acidic solution ofsparingly-soluble Group IIA complexes (“AGIIS”) and at least oneadditive. The AGIIS can be prepared by mixing a mineral acid (such assulfuric acid), and a Group IIA hydroxide (such as calcium hydroxide) ora Group IIA salt of a dibasic acid (such as calcium sulfate), or amixture of the two Group IIA compounds, followed by removing the solidformed. The additives can be an alcohol, an organic acid or asurface-active agent. The composition has various uses, includingcleaning, food production, decontamination, bioremediation, agriculturalapplication, medical application, and detoxification of substances.

Although not wanting to be bound by theory, one of ordinary skill in theart will understand that the term “pH” in the present invention pertainsmainly to the chemistry definition, wherein pH (short for potentiometrichydrogen ion concentration) is considered a measure of the acidity orbasicity of a solution. Although not wanting to be bound by theory, pHapproximates but is not equal to p[H], the negative logarithm (base 10)of the molar concentration of dissolved hydrogen ions (H+). Crudely,this matches the number of places behind the decimal point. For example0.1 molar hydrochloric acid (a strong acid) should be near pH 1 and0.0001 molar HCl should be near pH 4. Pure water is neutral, and can beconsidered either a very weak acid or a very weak base (center on the pHscale), giving it a pH of 7, or 0.0000001 M H⁺. For an aqueous solutionto have a higher pH, a base must be dissolved in it, which binds awaymany of these rare hydrogen ions. Hydrogen ions in water can be writtensimply as H⁺ or as hydronium (H₃O⁺) or higher species (e.g. H₉O₄ ⁺) toaccount for solvation, but all describe the same entity.

Although not wanting to be bound by theory, the pH of a weak acidsolution is calculated by means of an Initial-Change-Equilibrium Table(“ICE Table”). For acids with a pKa value greater than about 2, theformula to determine the approximated pH is as follows: [pH=½(pK_(a)−logc₀)]. Accordingly, the pH of a citric acid solution can be approximatedusing pKa=3.15; MW=192 g/mol. Namely:

-   -   a 25% (w/v) solution (˜1.34 M citric acid)        pH=½(3.15−log(1.34)=½(3.15−(0.127))=pH=˜1.5.    -   a 16% (w/v) solution (˜0.833 M citric acid)        pH=½(3.15−log(0.833)=½(3.15−(−0.07))=pH=˜1.61.    -   a 10% (w/v) solution (˜0.521 M citric acid)        pH=½(3.15−log(0.521)=½(3.15−(−0.283))=pH=˜1.99.

Similarly, the pH for dilutions of a less expensive weak organic acid(i.e. propionic acid) can be calculated using the pKa=˜4.88; 74.08g/mol; and density=0.99 g/ml. Namely,

-   -   a 25% (w/v) solution (˜3.37 M propionic acid)        pH=½(3.15−log(3.37)=½(4.88−(0.52))=pH=˜2.18.    -   a 16% (w/v) solution (˜2.15 M propionic acid)        pH=½(3.15−log(2.15)=½(4.88−(0.33))=pH=˜2.28.    -   a 10% solution (˜1.34 M propionic acid)        pH=½(4.88−log(1.34)=pH=½(4.88−(0.127))=pH=˜2.37.

Although not wanting to be bound by theory, the ability of such weakacids to kill frogs with ˜100% efficacy occurs when the pH of thesolution is less than about pH 2. In contrast, phytotoxicity of plantsoccurs with higher the concentration of the weak acid solution. As such,one object of the present invention is to utilize low concentrationsolutions of superacids alone, or as an organic acid pH adjuster tolower the pH of lower concentration weak acids without increasing itscorrosive potential. Although not wanting to be bound by theory, theaddition of a composition capable of lowering the pH of a weak acidsolution without increasing its corrosive potential can be a valuableproduct in many fields such as medicine, biology, chemistry, foodscience, environmental science, oceanography and many others, includingcompositions capable of being used as a low phytotoxic pesticide forCoqui frogs and other species. Additionally, one skilled in the artappreciates that the low phytotoxic acidic pesticides and method used tokill soft-bodied animals can be a lower cost, and more effectivealternative to many current methods used today without departing fromthe scope and spirit of the invention

SUMMARY

One aspect of the current application is an aqueous pesticidecomposition that comprises a propionic acid solution having aconcentration in the range of about 5.0% to 25%. The pH of thiscomposition is in the range of pH about 0.5 to about pH 3.0. The pH ofthe proprionic acid pesticide composition can be adjusted to within arange of pH 0.5 to pH 3.0 using an acidic calcium sulfate (ACS) solutionor a sulfuric acid solution. The pH adjusted propionic compositions canbe a liquid or a solid and both are lethal to Coqui frogs and Coqui frogeggs when contacted. These compositions may have mild phytotoxic effectson plants. In one embodiment, the aqueous pesticide composition has aproprionic acid concentration in the range of 5% to 15%, and a pH in therange of pH 0.8 to pH 2.5. In a preferred embodiment, the aqueouspesticide composition has a proprionic acid concentration in the rangeof 8% to 12%, and the pH in the range of pH 1.0 to pH 2.0. In a mostpreferred embodiment, the aqueous pesticide composition has a proprionicacid concentration of about 12% and the pH in the range of about pH 1.5.A surfactant can be added to the proprionic acid composition toincreases the surface area of the pesticide on the soft-bodied animal ofinterest.

A second aspect of the current application is an aqueous pesticidecomposition that comprises an Acidic Calcium Sulfate (ACS) solutionhaving a concentration in the range of about 5.0% to 25%. The ACScomposition can be a liquid or a solid and is lethal to Coqui frogs uponcontact. These ACS compositions can be a liquid or a solid and both arelethal to Coqui frogs and Coqui frog eggs when contacted. These ACScompositions may have mild phytotoxic effects on plants. The pH of thisACS composition is in the range of pH about 0.5 to about pH 3.0. The pHof the ACS pesticide composition can be adjusted to within a range of pH0.5 to pH 3.0 by adding a proprionic acid salt. In one embodiment, theaqueous pesticide composition has an ACS concentration in the range of5% to 15%, and a pH in the range of pH 0.8 to pH 2.5. In a preferredembodiment, the aqueous pesticide composition has an ACS concentrationin the range of 8% to 12%, and the pH in the range of pH 1.0 to pH 2.0.In a most preferred embodiment, the aqueous pesticide composition has aACS concentration of about 11.5% and the pH in the range of about pH1.5. A surfactant can be added to the ACS composition to increases thesurface area of the pesticide on the soft-bodied animal of interest.

A third aspect of the current application is an aqueous pesticidecomposition that comprises a citric acid solution having a concentrationin the range of about 5.0% to 25%. The pH of this composition is in therange of pH about 0.5 to about pH 3.0. The pH of the citric acidpesticide composition can be adjusted to within a range of pH 0.5 to pH3.0 using an acidic calcium sulfate (ACS) solution or a sulfuric acidsolution. The pH adjusted citric acid compositions can be a liquid or asolid and both are lethal to Coqui frogs and Coqui frog eggs whencontacted. These compositions may have mild phytotoxic effects onplants. In one embodiment, the aqueous pesticide composition has acitric acid concentration in the range of 5% to 16%, and a pH in therange of pH 0.8 to pH 2.5. In a preferred embodiment, the aqueouspesticide composition has a citric acid concentration in the range of 8%to 12%, and the pH in the range of pH 1.0 to pH 2.0. In a most preferredembodiment, the aqueous pesticide composition has a citric acidconcentration of about 12% and the pH in the range of about pH 1.5. Asurfactant can be added to the citric acid composition to increases thesurface area of the pesticide on the soft-bodied animal of interest. Forexample the soft bodied animals killed or repelled by the citric acidcomposition are tree frogs, cane toads, ants, termites, slugs, nettleand other caterpillars, nematodes, aphids, spider mites, fruit flylarva, varro mites of the honey bee, and other soft bodied insects thatare usually regarded as pests.

A fourth aspect of the current invention is a method of killing asoft-bodied animal of interest with a pesticide. The method involvescontacting the soft-bodied animal with the pesticide, wherein thepesticide is a propionic acid composition, a citric acid composition, oran ACS composition having a concentration in the range of 5.0% to 15%,and a pH in the range of pH 0.5 to pH 3.0. Part of the method includesspraying any of the previously mentioned pH adjusted pesticides an areainhabited by the soft-bodied animals of interest. In a specificembodiment, the soft-bodied animals of interest comprise Coqui frogs andCoqui frog eggs. Additionally, other soft bodied animals such as treefrogs, cane toads, ants, termites, slugs, nettle and other caterpillars,nematodes, aphids, spider mites, fruit fly larva, varro mites of thehoney bee, and other soft bodied insects that are usually regarded aspests are also killed by this method. One portion of this method mayinclude using lures or traps to encourage the soft-bodied animals ofinterest to inhabit the traps or lures prior to spraying the pesticidein small confined, yet specific areas. On a larger scale, the methodcontemplates filling various types of spraying apparatus with thepesticide and saturating entire areas where the pests are located. Morespecifically for smaller areas less than about 100 sq meters, a handsprayer or a garden sprayer with volumes less than about 10 liters willsuffice. However, larger areas (i.e. acreage) may need larger sprayerssuch as: Mounted Sprayer-Semi Hydraulic; Trailed Sprayer; MountedSprayer With Hydraulic Boom; Trailed Sprayer With High Wheel; TrailedSprayer High Wheel With Electronic Control Unit; Mounted Sprayer-BasicType; Mounted Sprayer-Basic Type With Clean Water Tank; Garden Sprayer;High Pressure Diaphragm Pump; Power Sprayer With Electric or FuelPowered Engine; Fertilizer Spreader; Inter row Rotary Cultivator; orfunctional equivalent thereof.

A fifth aspect of the current invention is a method of killing asoft-bodied animal of interest with a solid pesticide. The methodinvolves contacting the soft-bodied animal with the pesticide, whereinthe solid pesticide is a propionic acid composition, a citric acidcomposition, or an ACS composition having a concentration in the rangeof 5.0% to 15%, and a pH in the range of pH 0.5 to pH 3.0. Part of themethod includes positioning the dried solid of any of the previouslymentioned pH adjusted pesticides an area inhabited by the soft-bodiedanimals of interest. In a specific embodiment, the soft-bodied animalsof interest comprise Coqui frogs and Coqui frog eggs. Additionally,other soft bodied animals such as tree frogs, cane toads, ants,termites, slugs, nettle and other caterpillars, nematodes, aphids,spider mites, fruit fly larva, varro mites of the honey bee, and othersoft bodied insects that are usually regarded as pests are also killedby this method. However, before the solid pesticide can be placed, itmust be made. The propionic acid composition, a citric acid composition,or an ACS composition having a concentration in the range of 5.0% to15%, and a pH in the range of pH 0.5 to pH 3.0. can be mixed with amatrix, and allowed to dry. Some of the preferred matrix supportsinclude: bentonite clay, montmorillonite clay, phyllosilicate, bayerite,pseudoboehmite, alumina, silica gel, aluminum oxides, gibbisite,boehmite, porous glass, collagen, cellulose, etc.

BRIEF DESCRIPTION OF DRAWINGS

The following drawings form part of the present specification and areincluded to further demonstrate certain aspects of the presentinvention. The invention may be better understood by reference to one ormore of these drawings in combination with the detailed description ofspecific embodiments presented herein.

FIG. 1 shows an apparatus and method for killing frogs, and frog eggs onplants that will be either imported or exported.

DETAILED DESCRIPTION Terms

Before describing the present invention in detail, it is to beunderstood that this invention is not limited to particular compositionsor composition delivery systems, which may vary. One having ordinaryskill in the art will understand that the terminology used herein is forthe purpose of describing particular embodiments only, and is notintended to be limiting. In addition, before describing detailedembodiments of the invention, it will be useful to set forth definitionsthat are used in describing the invention. The definitions set forthapply only to the terms as they are used in this patent and may not beapplicable to the same terms as used elsewhere, for example inscientific literature or other patents or applications including otherapplications by these inventors or assigned to common owners.Additionally, when examples are given, they are intended to be exemplaryonly and not to be restrictive.

It must be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an” and “the” include plural referentsunless the context clearly dictates otherwise. Thus, for example,reference to “a pharmacologically active agent” includes a mixture oftwo or more such compounds, reference to “a base” includes mixtures oftwo or more bases, reference to “an acid” includes mixtures of two ormore acids, and the like.

In describing and claiming the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The terms “Active agent,” “chemically active agent,” “composition,” and“pestiscide” are typically used interchangeably herein to refer tocompositions and drugs that may be useful as a preservative and additivefor food and feed, as well as a pesticide for certain species. The termsalso encompass chemically acceptable, chemically active derivatives andanalogs of such compositions, including, but not limited to, salts,esters, amides, pro-drugs, active metabolites, inclusion complexes,analogs, and the like. Therefore, when the terms “active agent,”“chemically active agent”, or “pestiscide” are used, it is to beunderstood that applicants intend to include the active composition perse as well as chemically acceptable, pharmaceutically acceptable,pharmacologically active salts, esters, amides, pro-drugs, activemetabolites, inclusion complexes, analogs, etc., which are collectivelyreferred to herein as “chemically or pharmaceutically acceptablederivatives,” or “functional chemical derivatives thereof.”

The term “ACS-P” as used in the present invention pertains to theby-product created during the manufacture of Acidic Calcium Sulfate(“ACS”) according to the Mionix protocol. It consists of calcium sulfatesaturated with sulfuric acid and its production is described below.Another way of describing ACS-P is the calcium salt of sulfuric acidthat is highly saturated with sulfuric acid. When ACS 100, or 10N ACS,is manufactured the by-product has been called ACS-P 100. When ACS 50,or 5N ACS, is manufactured the by-product is called ACS-P 50.

The term “ACS” acidified calcium sulfate as used in the presentinvention pertains to acids, or acidic mixtures, used herein includeacidic solution of sparingly-soluble Group IIA complexes (“AGIIS”);adduct having AGIIS, preferably it is the organic acid adduct, whereinthe organic acid can be propionic acid, lactic acid, or both; sulfuricacid having calcium sulfate dissolved therein, the sulfuric acid can beconcentrated sulfuric acid; highly acidic metalated organic acid(“HAMO”); highly acidic metalated mixture of inorganic acid (“HAMMIA”),and a mixture thereof. A first acid, or acidic mixture, is AGIIS. Theacidic, or low pH, solution of sparingly-soluble Group IIA complexes(“AGIIS”) may have a suspension of very fine particles, and the term“low pH” means the pH is below 7, in the acidic region. The AGIIS has acertain acid normality but does not have the same dehydrating behavioras a saturated calcium sulfate in sulfuric acid having the samenormality. In other words, the AGIIS has a certain acid normality butdoes not char sucrose as readily as does a saturated solution of calciumsulfate in sulfuric acid having the same normality. Further, the AGIIShas low volatility at room temperature and pressure. It is lesscorrosive to a human skin than sulfuric acid saturated with calciumsulfate having the same acid normality. Not intending to be bound by thetheory, it is believed that one embodiment of AGIIS comprisesnear-saturated, saturated, or super-saturated calcium, sulfate anions orvariations thereof, and/or complex ions containing calcium, sulfates,and/or variations thereof.

The term “complex,” as used herein, denotes a composition whereinindividual constituents are associated. “Associated” means constituentsare bound to one another either covalently or non-covalently, the latteras a result of hydrogen bonding or other inter-molecular forces. Theconstituents may be present in ionic, non-ionic, hydrated or otherforms.

The term “surfactant,” as used herein, refers to a blend of surfaceactive agents that are usually organic amphiphilic compounds, meaningthey contain both hydrophobic groups (their “tails”) and hydrophilicgroups (their “heads”). Therefore, they are soluble in both organicsolvents and water. One of ordinary skill in the art understands thatsurfactants can be classified by the presence of formally charged groupsin its head. A non-ionic surfactant has no charge groups in its head(e.g. tween, triton x-100, cetyl alcohol etc). The head of an ionicsurfactant carries a net charge (e.g. Sodium dodecyl sulfate, CHAPS,benzalkonium chloride, etc). If the charge is negative, the surfactantis more specifically called anionic; if the charge is positive, it iscalled cationic. If a surfactant contains a head with two oppositelycharged groups, it is termed zwitterionic. Some surfactants that may beuseful for this invention include Perfluorooctanoate (PFOA or PFO);Perfluorooctanesulfonate (PFOS); Sodium dodecyl sulfate (SDS), ammoniumlauryl sulfate, and other alkyl sulfate salts; Sodium laureth sulfate,also known as sodium lauryl ether sulfate (SLES); Alkyl benzenesulfonate; Soaps, or fatty acid salts; Cationic (based on quaternaryammonium cations); Cetyl trimethylammonium bromide (CTAB) a.k.a.hexadecyl trimethyl ammonium bromide, and other alkyltrimethylammoniumsalts; Cetylpyridinium chloride (CPC); Polyethoxylated tallow amine(POEA); Benzalkonium chloride (BAC); Benzethonium chloride (BZT);Zwitterionic (amphoteric); CHAPS(3-[(3-Cholamidopropyl)dimethylammonio]-1-propanesulfonate); Dodecylbetaine; Cocamidopropyl betaine; Coco ampho glycinate; Nonionic; Alkylpoly(ethylene oxide); Polysorbates: based on Polyoxyethylene Glycol,including the Tween series (ex. Tween 20, Tween 80), the Brij series]],the [[ex. Triton detergent[Triton]] series (ex. Triton X-100);Alkylphenol poly(ethylene oxide); Copolymers of poly(ethylene oxide) andpolypropylene oxide) (commercially called Poloxamers or Poloxamines);Alkyl polyglucosides; Octyl glucoside; Decyl maltoside; Fatty alcohols;Cetyl alcohol; Oleyl alcohol; Cocamide MEA, cocamide DEA; Dodecyldimethylamine oxide

The term “sprayer,” as used herein, includes all types of sprayers forliquid and dry compositions. The sprayers contemplated include, but arenot limited to: Hand Spray Bottles with volumes less than about 1 liter;Garden Sprayer with volumes less than about 10 liters; MountedSprayer-Semi Hydraulic; Trailed Sprayer; Mounted Sprayer With HydraulicBoom; Trailed Sprayer With High Wheel; Trailed Sprayer High Wheel WithElectronic Control Unit; Mounted Sprayer-Basic Type; MountedSprayer-Basic Type With Clean Water Tank; Garden Sprayer; High PressureDiaphragm Pump; Power Sprayer With Electric or Fuel Powered Engine;Fertilizer Spreader; Interrow Rotary Cultivator. One of ordinary skillin the art will understand that any type of sprayer capable of sprayingliquid or dry chemicals may be used for this invention.

The term “propionic acid,” as used herein, denotes propionic acid, andother derivatives having a functional chemical equivalents havingsimilar structures to H(CH₂)—COOH acid. Other names for propionic acidinclude: Carboxyethane, Ethanecarboxylic acid, Ethylformic acid,Metacetonic acid, Methyl acetic acid, Propanoic acid. Propionic acid hasphysical properties intermediate between those of the smaller carboxylicacids, formic and acetic acids, and the larger fatty acids. It ismiscible with water, but can be removed from water by adding salt. Aswith acetic and formic acids, it consists of hydrogen bonded pairs ofmolecules both as the liquid and vapor. Propionic acid displays thegeneral properties of carboxylic acids, wherein it can form amide,ester, anhydride, and chloride derivatives, all of which are included asfunctional equivalents. It can undergo alpha-halogenation with brominein the presence of PBr₃ as catalyst (the HVZ reaction) to formCH₃CHBrCOOH. Currently the world's largest producer of propionic acid isBASF, with approximately 80 kt/a production capacity.

The term “acidity regulators”, or “pH control agents” are generallydenoted as food additives used to change or maintain pH (acidity orbasicity) in a composition. They can be organic or mineral acids, bases,neutralizing agents, or buffering agents.

Preferred Embodiments

One aspect of the present invention pertains to a method employing anacidified pesticide to reduce, inhibit, or eradicate a large or smallinfestation that has resulted in a population growth of an invasivespecies of frog or other living soft-bodied organism, wherein theacidified pesticide has a minimum phytotoxic effect on local flora andfauna. Here an effective amount (i.e. in that the amount is sufficientto exert its lethal pesticide properties) of the composition is allowedto contact (e.g. such as by drenching, setting, laying, mixing, mistingor spraying) the infestation area.

Although not wanting to be bound by theory, no absolute methods areavailable for completely eliminating invasive species in otherenvironments without some adverse effects to some plants, animals,insects, fowls, reptiles, and the like, however, the acidified pesticidecomposition and method thereof do offer a economical and practicalsolution for reducing the population of an infestation area withoutsignificant damage to local flora and fauna. The compositions andmethods of making and using acidic pesticides are described in theexamples below:

EXAMPLES

The following examples are provided to further illustrate this inventionand the manner in which it may be carried out. It will be understood byone of ordinary skill in the art, however, that the specific detailsgiven in the examples have been chosen for purposes of illustration onlyand not be construed as limiting the invention.

Example 1 Acids

Acidic Calcium Sulfate (“ACS”).

A preferred method of preparing AGIIS involves mixing a mineral acidwith a Group IIA hydroxide, or with a Group IIA salt of a dibasic acid,or with a mixture of the two Group IIA materials. In the mixing, a saltof Group IIA is also formed. Preferably, the starting Group IIA materialor materials selected will give rise to, and form, the Group IIA salt orsalts that are sparingly soluble in water. The preferred mineral acid issulfuric acid, the preferred Group IIA hydroxide is calcium hydroxide,and the prefer Group IIA salt of a dibasic acid is calcium sulfate.Other examples of Group IIA salt include calcium oxide, calciumcarbonate, and “calcium bicarbonate.”

Thus, for example, AGIIS can be prepared by mixing or blending startingmaterials given in one of the following scheme with goodreproducibility:

(1) H₂SO₄ and Ca(OH)₂;

(2) H₂SO₄, Ca(OH)₂, and CaCO₃;

(3) H₂SO₄, Ca(OH)₂, CaCO₃, and CO₂ (gas);

(4) H₂SO₄, CaCO₃, and Ca(OH)₂;

(5) H₂SO₄, Ca(OH)₂, and CaSO₄;

(6) H₂SO₄, CaSO₄, CaCO₃, and Ca(OH)₂;

(7) H₂SO₄, CaSO₄, CaCO₃, and CO₂ (gas); and

(8) H₂SO₄, CaSO₄, CaCO₃, CO₂ (gas), and Ca(OH)₂.

Preferably, AGIIS is prepared by mixing calcium hydroxide withconcentrated sulfuric acid, with or without an optional Group HA salt ofa dibasic acid (such as calcium sulfate) added to the sulfuric acid. Theoptional calcium sulfate can be added to the concentrated sulfuric acidprior to the introduction of calcium hydroxide into the blendingmixture. The addition of calcium sulfate to the concentrated sulfuricacid appears to reduce the amount of calcium hydroxide needed for thepreparation of AGIIS. Other optional reactants include calcium carbonateand gaseous carbon dioxide being bubbled into the mixture. Regardless ofthe use of any optional reactants, it was found that the use of calciumhydroxide is desirable.

One preferred method of preparing AGIIS can be described briefly as:Concentrated sulfuric acid is added to chilled water (8°-12° C.) in thereaction vessel, then, with stirring, calcium sulfate is added to theacid in chilled water to give a mixture. Temperature control isparamount to this process. To this stirring mixture is then added slurryof calcium hydroxide in water. The solid formed from the mixture is thenremoved. This method involves the use of sulfuric acid, calcium sulfate,and calcium hydroxide, and it has several unexpected advantages.Firstly, this reaction is not violent and is not exceedingly exothermic.Besides being easy to control and easy to reproduce, this reaction usesingredients each of which has been reviewed by the U.S. Food and DrugAdministration (“U.S. FDA”) and determined to be “generally recognizedas safe” (“GRAS”). As such, each of these ingredients can be addeddirectly to food, subject, of course, to certain limitations. Underproper concentration, each of these ingredients can be used asprocessing aids and in food contact applications. Their use is limitedonly by product suitability and Good Manufacturing Practices (“GMP”).The AGIIS so prepared is thus safe for animal consumption, safe forprocessing aids, and safe in food contact applications. Further, theAGIIS reduces biological contaminants in not only inhibiting the growthof, and killing, microorganisms but also destroying the toxins formedand generated by the microorganisms. The AGIIS formed can also preserve,or extend the shelf-life of, consumable products, be they plant, animal,pharmaceutical, or biological products. It also preserves or improvesthe organoleptic quality of a beverage, a plant product or an animalproduct. It also possesses certain healing and therapeutic properties.

The sulfuric acid used is usually 95-98% FCC Grade (about 35-37 N). Theamount of concentrated sulfuric acid can range from about 0.05 M toabout 18 M (about 0.1 N to about 36 N), preferably from about 1 M toabout 5 M. It is application specific. The term “M” used denotes molaror moles per liter.

Normally, a slurry of finely ground calcium hydroxide suspended in water(about 50% of w/v) is the preferred way of introducing the calciumhydroxide, in increments, into a stirring solution of sulfuric acid,with or without the presence of calcium sulfate. Ordinarily, thereaction is carried out below 40° C., preferably below room temperature,and more preferably below 10° C. The time to add calcium hydroxide canrange from about 1 hour to about 4 hours. The agitation speed can varyfrom about 600 to about 700 rpm or higher. After the mixing, the mixtureis filtered through a 5 micron filter. The filtrate is then allowed tosit overnight and the fine sediment is removed by decantation.

The calcium hydroxide used is usually FCC Grade of about 98% purity. Forevery mole of concentrated acid, such as sulfuric acid, the amount, inmole, of calcium hydroxide used is application specific and ranges fromabout 0.1 to about 1.

The phosphoric acid used is usually from JT Baker of about 85-88%.

The calcium monohydrogen phosphate is usually of 98-99%; and the calciumphosphate (“the tribasic”) is obtained from Mallinckrodt. Otherphosphate salts used are all of reagent grade.

The optional calcium carbonate is normally FCC Grade having a purity ofabout 98%. When used with calcium hydroxide as described above, forevery mole of concentrated acid, such as sulfuric acid, the amount, inmole, of calcium carbonate ranges from about 0.001 to about 0.2,depending on the amount of calcium hydroxide used.

The optional carbon dioxide is usually bubbled into the slurrycontaining calcium hydroxide at a speed of from about 1 to about 3pounds pressure. The carbon dioxide is bubbled into the slurry for aperiod of from about 1 to about 3 hours. The slurry is then added to thereaction vessel containing the concentrated sulfuric acid.

Another optional ingredient is calcium sulfate, a Group IIA salt of adibasic acid. Normally, dihydrated calcium sulfate is used. As used inthis application, the phrase “calcium sulfate,” or the formula “CaSO₄,”means either anhydrous or hydrated calcium sulfate. The purity ofcalcium sulfate (dihydrate) used is usually 95-98% FCC Grade. The amountof calcium sulfate, in moles per liter of concentrated sulfuric acidranges from about 0.005 to about 0.15, preferably from about 0.007 toabout 0.07, and more preferably from about 0.007 to about 0.04. It isapplication specific.

In the event that CaSO₄ is used for the reaction by adding it to thesolution of concentrated H₂SO₄, the amount of CaSO₄, in grams per literof solution based on final volume, has the following relationship:

Final AGIIS Acid Normality (N) Amount of CaSO₄ in g/l 1-5 5  6-10 411-15 3 16-20 2 21-36 1

The AGIIS obtained could have an acid normality range of from about 0.05to about 31; the pH of lower than 0; boiling point of from about 100 toabout 106° C.; freezing point of from about −8° C. to about 0° C. AGIISobtained from using the reaction of H₂SO₄/Ca(OH)₂/CaSO₄ had thefollowing analyses (average):

AGIIS with Final Acid Normality of 1.2 N, pH of −0.08

H₃O⁺, 2.22%; Ca, 602 ppm; SO₄, 73560 ppm; K, 1.36 ppb; impurities of19.68 ppm, and neither Na nor Mg was detected.

AGIIS with Final Acid Normality of about 29 N, pH of about −1.46

H₃O⁺, 30.68%; Ca, 52.9 ppm; SO₄, 1422160 ppm; K, 38.02 ppb; and neitherNa nor Mg was detected.

Aqueous solutions of other alkalis or bases, such as Group IA hydroxidesolution or slurry and Group IIA hydroxide solution or slurry can beused. Groups IA and IIA refer to the two Groups in the periodical table.The use of Group IIA hydroxide is preferred. Preferably, the saltsformed from using Group IIA hydroxides in the reaction are sparinglysoluble in water. It is also preferable to use only Group IIA hydroxideas the base without the addition of Group IA hydroxide. After thereaction, the resultant concentrated acidic solution with a relativelylow pH value, typically below pH 1, can then be diluted with de-ionizedwater to the desired pH value, such as pH of about 1 or about 1.8.

As discussed above, AGIIS has relatively less dehydrating properties(such as charring sucrose) as compared to the saturated solution ofCaSO₄ in the same concentration of H₂SO₄. Further, the stability andnon-corrosive nature of the AGIIS of the present invention can beillustrated by the fact that a person can put his or her hand into thissolution with a pH of less than 0.5 and, yet, his or her hand suffers noirritation, and no injury. If, on the other hand, one places his or herhand into a solution of sulfuric acid of pH of less than 0.5, anirritation would occur within a relatively short span of time. Asolution of 28 N of sulfuric acid saturated with calcium sulfate willcause chemical burn to a human skin after a few seconds of contact. Incontrast, AGIIS solution of the same normality would not cause chemicalburn to a human skin even after in contact for 5 minutes. The AGIIS doesnot seem to be corrosive when being brought in contact with theenvironmental protective covering of plants (cuticle) and animals(skin). AGIIS has low volatility at room temperature and pressure. Evenas concentrated as 29N, the AGIIS has no odor, does not give off fumesin the air, and is not irritating to a human nose when one smells thisconcentrated solution.

A second acid, or acidic mixture, is an adduct having AGIIS, whichcomprises AGIIS and one more additives. The “additive” of the presentinvention appears to enhance, and also appears to be synergistic to, theeffectiveness of the acidic composition of the present invention.Examples of the additive include alcohol, organic acid, periodic acid,and surfactant. The amount of additive added to the AGIIS variesdepending on the desired final weight percent of the additive in thefinal adduct composition. The weight percent of additive needed for theadduct composition of the present invention can vary from about 0.01 toabout 99.99, based on the total weight of the final adduct composition.The alcohol additive preferred for the present invention includesmethanol, ethanol, 1-propanol, 2-propanol, and other lower alkylalcohols.

Organic acid additive of the present invention includes carboxylic acid.A carboxylic acid is an organic compound containing the —COOH group,i.e., a carbonyl attached to a hydroxyl group. Preferred organic acidsfor the present invention include lactic acid, acetic acid, propionicacid, oxalic acid, sorbic acid, butyric acid, benzoic acid, glycolicacid, peracetic acid, and a mixture thereof.

A surfactant for the present invention is a surface-active agent. It isusually an organic compound consisting of two parts: One, a hydrophobicportion, usually including a long hydrocarbon chain; and two, ahydrophilic portion which renders the compound sufficiently soluble ordispersible in water or another polar solvent. Surfactants are usuallyclassified into: (1) anionic, where the hydrophilic moiety of themolecule carries a negative charge; (2) cationic, where this moiety ofthe molecule carries a positive charge; and (3) non-ionic, which do notdissociate, but commonly derive their hydrophilic moiety frompolyhydroxy or polyethoxy structures. Other surfactants includeampholytic and zwitterionic surfactants. A preferred surfactant for thepresent invention includes polysorbates (Tween 80).

Unless otherwise defined, the amount of each ingredient or component ofthe present invention is based on the weight percent of the finalcomposition, usually the concentrate before further dilution to achievethe desired pH of about 1.8. The AGIIS having a pH of about 1.8 isusually further diluted with water before applying to an animal productor a plant product.

A third acid, or acidic mixture, is highly acidic metalated organic acid(“HAMO”). The HAMO composition may have a suspension of very fineparticles, and it has a monovalent or a polyvalent cation, an organicacid, and an anion of a regenerating acid, such as the anion of a strongoxyacid. The term “highly acidic” means the pH is in the acidic region,below at least about 4. HAMO of the present invention is less corrosiveto a ferrous metal than a solution of a mineral acid having the sameacidic pH value as that of the acidic composition. HAMO is also morebiocidal than a mixture of the organic acid and a metal salt of theorganic acid which mixture having the same acid normality value as thatof the acidic composition.

Broadly, one way HAMO can be prepared is by mixing the followingingredients: (1) at least one regenerating acid; (2) at least one metalbase; and (3) at least one organic acid, wherein the equivalent amountof the regenerating acid is in excess of the equivalent amount of themetal base. The equivalent amount of the metal base should be aboutequal to that of the organic acid. Instead of using a metal base and anorganic acid, a metal salt of the organic acid can be used in place ofthe metal base and the organic acid. The insoluble solid is removed byany conventional method, such as sedimentation, filtration, orcentrifugation.

Generally, HAMO can be prepared by blending or mixing the necessaryingredients in at least the following manners:

1. Regenerating acid+(metal base+organic acid);

2. Regenerating acid+(metal base+salt of organic acid);

-   3. (Regenerating acid+salt of organic acid)+base; and

4. Regenerating acid+salt of organic acid.

The parenthesis in the above scheme denotes “pre-mixing” the twoingredients recited in the parenthesis. Normally, the regenerating acidis added last to generate the HAMO. Although each of the reagents islisted as a single reagent, optionally, more than one single reagent,such as more than one regenerating acid or organic acid, can be used inthe current invention. The number of equivalents of the regeneratingacid must be larger than the number of equivalents of the metal base, orthose of the metal salt of the organic acid. When the organic acid is anamino acid, which, by definition contains at least one amino group, thenthe number of equivalents of the regenerating acid must be larger thanthe total number of equivalents of the metal base, or metal salt of theorganic acid, and the “base” amino group of the amino acid. Thus, theresultant highly acidic metalated organic acid is different from, andnot, a buffer.

As used herein, a regenerating acid is an acid that will “re-generate”the organic acid from its salt. Examples of a regenerating acid includea strong binary acid, a strong oxyacid, and others. A binary acid is anacid in which protons are directly bound to a central atom, that is(central atom)-H. Examples of a binary acid include HF, HCl, HBr, HI,H₂S and HN₃. An oxyacid is an acid in which the acidic protons are boundto oxygen, which in turn is bound to a central atom, that is (centralatom)-O—H. Examples of oxyacid include acids having Cl, Br, Cr, As, Ge,Te, P, B, As, I, S, Se, Sn, Te, N, Mo, W, or Mn as the central atom.Some examples include H₂SO₄, HNO₃, H₂SeO₄, HClO₄, H₃PO₄, and HMnO₄. Someof the acids (e.g. HMnO₄) cannot actually be isolated as such, but occuronly in the form of their dilute solutions, anions, and salts. A “strongoxyacid” is an oxyacid which at a concentration of 1 molar in watergives a concentration of H₃O⁺ greater than about 0.8 molar. Theregenerating acid can also be an acidic solution of sparingly-solubleGroup IIA complexes (“AGIIS”).

A fourth acid, or acidic mixture, is a highly acidic metalated mixtureof inorganic acids (“HAMMIA”). The composition has an acidic pH, and canbe isolated from a mixture prepared by mixing ingredients comprising asalt of phosphoric acid, and a preformed, or in-situ generated, solutionor suspension of an acidic sparingly-soluble Group IIA complex(“AGIIS”), wherein the solution or suspension of AGIIS is in an amountsufficient to render the acidic pH of the composition to be less thanabout 2.

Each of the acid mixtures are the subject of the following U.S. Patentsand hereby incorporated by reference:

-   1. U.S. Pat. No. 7,323,436 titled: “Adduct having an acidic solution    of sparingly-soluble group IIA complexes,” issued to Kemp et al., on    Jan. 29, 2008.-   2. U.S. Pat. No. 6,902,753 titled: “Acidic solution of    sparingly-soluble group IIA complexes,” issued to Kemp et al., on    Jun. 7, 2005.-   3. U.S. Pat. No. 6,881,424 titled: “Highly acidic metalated organic    acid,” issued to Kemp et al., on Apr. 19, 2005.-   4. U.S. Pat. No. 6,808,730 titled: “Highly acidic metalated organic    acid as a food additive,” issued to Kemp et al., on Oct. 26, 2004.-   5. U.S. Pat. No. 6,572,908 titled: “Highly acidic metalated organic    acid as a food additive,” issued to Kemp et al., on Jun. 3, 2003.-   6. U.S. Pat. No. 6,436,891 titled: “Adduct having an acidic solution    of sparingly-soluble group IIA complexes,” issued to Kemp et al., on    Aug. 20, 2002.

One having ordinary skill in the art will recognize that Acidic CalciumSulfate (“ACS”) acids, as described above, are acid products that arefound in nature, but can be manufactured in many ways. Such manufacturedacids are considered to be functional chemical equivalents of the ACSacids described herein. For example, Hydrite Chemical Corporation (4031Alvis Ct, Rocklin, Calif. 95677) manufactures a product for the MionixCorporation called ACS 100 and ACS 50. These commercially manufacturedproducts can be used to produce the product of this invention or as acidacidulant for different organic acids.

Although not wanting to be bound by theory. The ACS compositions areakin to citric acid as they appear on the EPA's list of inertingredients, 4a or 4b, which can be used as a pesticide because of theminimal risk they pose to the environment. Propionic acid and its saltsalso appear on list 4b as does sulfuric acid, whereas calcium sulfate,dehydrate or hemihydrate, appears on list 4a. In fact, the use of ACS asan acidulant potentiates citric acid and makes it possible to use alower concentration. ACS or another functional equivalent acidulant canalso be used with citric acid or regenerate citric acid from its salt,which allows citric acid to be used at lower concentrations withoutdecreasing its lethal potential to frogs.

Example 2 Agent Green™

This example shows how an approximate 12% by volume Acidic CalciumSulfate can be used as a pH adjustor for agricultural uses. Thissolution can be marketed under a trade name of AGENT GREEN™, which ismade from ingredients generally regarded as safe (“GRAS”) by the FDA.Although not wanting to be bound by theory, Agent Green is a pH adjusterthat increases the acidity and lowers the pH activity of water. It hasmany agricultural applications including but not limited to adjustinghydroponics growing medium, soil acidity, and sanitizing surfaces. Oneof the concentrated products can also be used to remove rust from ironand steel. It also has many of the same properties as citric acid,however it is less corrosive than citric acid. When properly diluted (pH2.5) it can also be used as a plant nutrient to add calcium via foliarapplication.

Materials: Strong plastic or stainless steel scoop, stirring stick, 5gal plastic bucket/container, scale with 10 lb capacity, pH meter orlitmus sticks, goggles, plastic coveralls. (Be sure to use goggles andplastic coveralls to protect your eyes and cotton clothing when mixingconcentrate.) Begin by adding 1.5-2 lbs of concentrate (calcium sulfatesaturated with sulfuric acid) to one gallon of tap or catchment water.Always add product to water instead of adding water to product. Stiruntil well mixed. The ratio of 1.5 lbs of product per gallon of waterwill produce a pH of approximately 1.3. When product is mixed with waterit immediately lowers the pH of the water while the white sedimentquickly falls to the bottom of the mixing container. Depending upon yourneeds, you may obtain any acidity level or pH of water by adding more orless concentrates. (For example 2 lbs of concentrate per gallon of waterwill produce water with a pH below 1.0 whereas 1 lb of product pergallon of water will produce a pH of approximately 1.5-1.75. Aftermixing the product, pour off the low pH water leaving the white sedimentin the container (also referred to by some as “white dirt”) and safe foruse as a soil amendment for plants that thrive in acidic soil. CAUTION:Agent Green concentrate is highly acidic as packaged in the container.The concentrate has little to no effect on the healthy skin of humans oranimals; however it will damage cotton, cement, and certain metals. Usecaution when mixing or applying concentrated solution of Agent Green.Use of the product with precipitant in suspension may clog a sprayer. Ifsprayer has metal parts rinse thoroughly after using. Applying a low pH(below 2.0 pH) to plants may result in harm to sensitive plants.Pre-test your plant for sensitivity. The active agent green has ACS inthe range of about 3%-about 20%. The preferred active agent green hasACS in the range of about 5%-about 15%, and the most preferred activeagent green has an ACS solution in the range in the about 10%-about 12%.The active agent green has a pH in the range of pH above 0 to about pH3. The preferred active agent green has pH in the range of about pH1-about pH 2.5, and the most preferred active agent green has a pHsolution in the range about pH 1.5-about pH 2.0.

Minor irritation may occur if product is allowed to come into contactwith eyes, cuts, or the mucus membranes of the nose and mouth. If anexposed area becomes irritated, rinse thoroughly with water untilirritation subsides. Seek medical attention as needed. When mixing orapplying concentrated product wear impervious protective clothing,including protective eyewear and use respirator or NIOSH recommendedmask for applying chemicals when applying product as a fine mist. Avoidinhalation of product spray mist as irritation of the respiratory tractmay result. Store with hazardous materials and keep out of reach ofchildren.

Example 3 Agent Green™ Plant Finisher and Agriculture Acidulant (Solid)

AGENT GREEN™ plant finisher is a solid acidulant. This means itincreases the acidic activity that results in compounds and dilutesolutions capable of lowering the pH of water by adding hydrogen ionactivity. It is useful for any agricultural application wherein thedesired purpose is to lower the pH, or increase the acidity, of water.Application of acidic water to soil lowers the pH of the soil andfacilitates plant absorption of nitrogen. This product contains addedcalcium and when applied to plant foliage as a spray it acts as a plantnutrient. When added to hydroponics growing medium or the water of fishor shrimp ponds this product will increase acidity and lower pH withoutadding any ingredients that are harmful.

Mix 1.5 lbs Acidic Calcium Sulfate (“ACS”) solid product (calciumsulfate saturated with sulfuric acid) with one gallon of water. Stirwell. After white precipitant falls to bottom of mixing container (takesabout 5 to 10 minutes) decant or pour off clear liquid into a secondarycontainer. The resulting liquid will be very acidic and have a pH ofapproximately 1.5. A litmus stick or pH meter can be use to monitor thepH activity, wherein more product or water can be added to reach theacidic strength desired. Use product as desired. If this product is usedas a foliar spray be sure to use only the clear liquid as product mayotherwise clog your sprayer. For best results, use product with an allplastic sprayer. If sprayer has metal parts rinse thoroughly afterusing. Spray clear liquid directly onto plant foliage or soil.

When mixed as directed, the resultant liquid has a pH of approximately1.5 and is highly acidic having properties similar to those of citricacid however it is less corrosive than higher concentrations of citricacid having the pH lowered by the Agent Green™. In order to avoidpossible harm to your plants test plant for sensitivity prior toapplication. If unsure of your plants sensitivity rinse the product offplant within thirty minutes of application. Hearty sun loving plantssuch as palms may tolerate the solution well whereas shade loving broadleaf or succulent plants such as bromeliads are more likely to be burnedby the solution unless further dilutions are made by adding additionalwater. For sensitive plants try using one pound of product in two or upto five gallons of water as needed according to plant requirements.Heavy sprays may be used with hearty plants or application to the groundwhereas a fine mist spray should be used with more sensitive plants. Ifplant shows signs of burns within about 12-48 hours of use diluteproduct further or discontinue use.

Minor irritation may occur if product is allowed to come into contactwith eyes, cuts, or the mucus membranes of the nose and mouth. Wearimpervious protective clothing, including eyewear, gloves, and boots asappropriate to prevent contact with eyes, skin and the mucus membranesof nose and mouth when mixing or applying this product. If an exposedarea becomes irritated, rinse with water until irritation subsides. Seekmedical attention as needed. Product will damage cotton clothing andmost metals and cement. It does not damage polyester clothing.

The active agent green solid can be mixed to have a solution of ACS inthe range of about 5%-about 20%. The preferred active agent green hasACS in the range of 8%-15%, and the most preferred active Agent Green™has an ACS solution in the range of about 10%-about 12%. The activeagent green has a pH in the range of pH above 0 to about pH 3. Thepreferred active Agent Green™ has pH in the range of about pH 1-about pH2.5, and the most preferred active agent green has a pH solution in therange about pH 1.5-about pH 2.0.

Example 4 Phytogenic Friendly Coqui Frog Pestiside

In view of the need to find new phytogenic friendly alternatives forcontrolling the spread of Coqui frogs, a commercially available foodsanitation product (i.e. Acidic Calcium Sulfate (“ACS”) was evaluatedfor inclusion in the current inventory of chemicals that can be appliedas sprays. ACS and functional equivalents thereof are made fromingredients that are generally regarded as safe (“GRAS”), and isapproved for use in food by the FDA and USDA. Although not wanting to bebound by theory, the efficacy of this product stems from its very uniquecharacteristic of being able to donate a very high activity of hydrogenions (low pH), while at the same time, having very low oxidative effectson plants and human skin. For example, a five (5) normal concentrationof ACS having a pH of approximately zero may be held in the human handwithout harm to the person holding the acid. In contrast, when verysmall amounts are applied to the skin of Coqui frogs it is quicklyabsorbed and respiration is immediately impaired with lethal results.Results of a field study using one hundred Coqui frogs showed about 95%of all frogs were killed within fifteen minutes when sprayed with aslittle as 1.0 ml of this an approximate ˜11.5% by volume solution ofACS.

Phytotoxicity of the dilute ACS solution used varied from none tomoderate, depending on the plant variety and could be minimizeddepending on the use of a mist versus heavy spray. Most if not allphytotoxic effects could be eliminated by rinsing the plant withinthirty minutes following application of the dilute ACS solution. Thereare many benefits to this product and the balance of frog lethalityversus phytotoxicity indicates ACS is a minimal risk pesticide againstthe Coqui frog infestation.

Commercially available ACS can be utilized as a pH modulator that is abactericidal GRAS product approved for use in food by the FDA and USDA.It is effective in removing E-Coli, Salmonella, Listeria, Campylobacterand other harmful bacteria from food. The platform product isalternately formulated for use with meat, fish, produce, pharmaceuticalsand more. The power of this product resides in its very uniquecharacteristic of having both a very high concentration of hydrogen ions(pH of approximately zero at a 5N concentration) while at the same timevery low corrosiveness. A 5N concentration of this product having a pHof approximately zero can be held in the palm of one's hand withoutharm. In contrast, for Coqui frogs, it's another story for when even avery small amount of this low pH product comes into contact with thefrogs skin it is quickly absorbed and immediately impacts respiratoryfunction, having lethal effects.

Example 5 Cost Effective Coqui Frog Pestiside

The use of ACS-P has been shown to be a cost-effective and non-toxicmeans for controlling the spread of Coqui, as determined by a three partfield study that was devised to I) determine the lethality of theproduct on individual frogs and klatches of eggs; II) test the productas a substitute for citric acid in a commercial application; III) applythe product in a residential setting to observe for phytotoxicity andreduction of Coqui noise.

A total of one hundred male and female adult and adolescent Coqui frogswere hand-captured from banana trees in groups of twenty over afive-week period. Upon capture frogs were collectively placed in a largeplastic container and then individually moved to 8 oz covered Styrofoamcups, approximately thirty minutes later.

At the bottom of each cup was a 2×2 inch double thickness layer of papertowel saturated with 2 ml of water. Ten minutes after being placed inthe cups, each frog was then inoculated with 1.0 ml of an about 11.5% byvolume solution of ACS-P in tap water using about 1.0 ml auto-pipetteand observed for fifteen minutes. Egg klatches were also recovered fromthe banana trees and divided into groups of approximately ten each. Onegroup was sprayed with 2 ml of product and one group was untreated. Theeggs were observed over two-three weeks.

Except for the largest of the female frogs, about 95% of all frogsexpired within a fifteen minutes of inoculation of 1.0 ml of theproduct. Some of the larger male frogs required an additional ml tocause death within an additional fifteen-minute period whereas many ofthe smaller adolescent frogs expired almost instantly. Some of the largefemales that were nearly two inches in length, required inoculation ofup to four ml of product before lethality was achieved. It was theorizedthat these females were more resistant to the product due to higherlevels of hydration. It was also determined that once sprayed, affectedand/or dead appearing frogs could not be revived by immersing them inwater. Most of the untreated eggs hatched whereas none of the treatedeggs hatched.

Example 6 Large Scale Field Test of Lethal and Phytotoxicity

Large-scale examples of the product's use and phytotoxicity at the sameconcentration (about 11.5%) as used in previous examples were alsoconducted by Palms of Hawaii. A five-gallon back pack sprayer equippedwith a mist spray nozzle was used to spray mature Palm trees beingprepared for distribution with about a gallon of spray each.

Upon spraying palm trees having frogs, frogs leap off the root balls andcrowns and from the junctions between the fronds and tree trunks. Thenurseryman rated the complete removal, if not extermination of all frogsfrom the trees as excellent. He was especially pleased because the ACS-Phad no phytotoxic consequences to the trees. Citric acid typicallycauses browning. Additionally, ants were also driven off the trees.

Following these tests of lethality, tests for phytotoxicity werecompleted, wherein approximately 500 gallons of ACS-P was applied usinga heavy spray nozzle to a ¼ acre yard that is densely covered withvarious kinds of trees and under growth having a healthy population ofCoqui frogs. Plants were observed for phytotoxic effects over a one-weekperiod. Phytotoxicity was found to vary from none to moderate accordingto the variety of plant. Bromeliads and tender shade-loving plants werefound to have yellowed leaves and in some cases brown spots where thespray had made a puddle. More hardy sun-loving plants having thick orwaxy leaves were not affected. Additionally, phytotoxic effects can beminimized by using a mist versus heavy spray that doesn't puddle on theleaves, or entirely eliminated by washing the product off the plant withplain water within 30 minutes of application.

In general, the product is designed to come into direct contact with thefrog by the spray in order to have lethal effects on the frog. However,surfaces that have accumulated a dried paste of ACS without rinsing ordilution are also lethal to frogs. For example, Styrofoam cupscontaining dried paste product retained its lethal potential, even afterthree months.

Using a survey of residents living near the treated field confirmedunanimously that the treated area was noticeably quieter for about 2-3weeks. Afterwards, it is believed that an existing population ofunsprayed frogs in neighboring areas moved into the now frog-freetreated area. Rainfall in this area is quite heavy so the effects of theproduct were assumed to be lost within a few days.

The results of this field study indicate that ACS-P (calcium sulfatesaturated with sulfuric acid) produced satisfactory results with frogand noise levels in treated areas. A very desirable quality of thisproduct is that the solution can be easily modified to vary theconcentration of hydrogen and calcium ions. An optimal balance of thesetwo elements will result in a solution that is at once lethal to thefrogs yet lacking significant phytotoxicity, and may even act as anutrient to most plants. The solution strength used in this study (e.g.about 11.5% ACS) is the preferred embodiment for a tropical area likeHawaii. However, one skilled in the art will understand that thisformulation can be varied and modified to encompass different frogs,flora, and fauna in different Geographic areas around the world. Suchmodifications of this preferred embodiment is considered to be withinthe spirit and scope of the application.

Given the efficacy found herein and the fact that ACS-P is made fromcomponents generally regarded as safe (“GRAS”) and have approval by theFDA and USDA for use in food, ACS-P should be considered for emergencyapproval by the EPA as a minimal risk pesticide to replace hydratedlime.

Example 7 Phytogenic Friendly Insecticide

The advantages of using superacids as pH adjusters, such as ACS an ACS-Pare many. ACS-P is less expensive than citric acid and less hazardous toapply than hydrated lime in combating Coqui frogs. Additionally, theseACS compositions have a number of other potential uses. For example, thelower concentrations and higher pH solutions of ACS can be used as apesticide for soft-bodied insects and can serve a second use as a plantnutrient to supply calcium via foliar feeding. Additionally, a solutionstrength having a pH of 1.8, which may be too high to kill some frogs,was effective in killing soft-bodied insects such as aphids and spidermites with minimal phytotoxicity to a Hibiscus plant. At a slightlyhigher concentration, and when sprayed with approximately 5 ml ofproduct, brown hump back slugs were killed.

In development of the current invention it was also found that ACSalone, or propionic acid having the pH adjusted with ACS also kills treefrogs, cane toads, slugs, including brown or humpback slugs, Africansnails, nettle and other caterpillars, nematodes, aphids, spider mites,fruit fly larva, and other miscellaneous soft bodied insects that areusually regarded as pests. It also drives off or repels fire ants andtermites yet does not appear to harm grasshoppers or lizards. Alsoimmerging on the scene is the honey bee mite known as the Varroa Mite,wherein one drop of this product instantly killed these mites. ACS inwater can also inhibit the growth of powdery mildew. When formulated asslurry or suspended in a carrier product such as bentonite clay orvermiculite, this product may be used to form barriers to repel theCoqui frog and other pests. The liquid solution of the product may alsobe used to inhibit the growth of harmful bacteria such as E-coli,salmonella, and simple rot bacteria present on post-harvest fruit,produce and food preparation surfaces, however the antimicrobialproperties for some of the ingredients of this pesticide are clearlyestablished under other patents. The Coqui frog is presently causing themost concern because it is threatening the export of agriculturalproducts from Hawaii to the US Mainland as well as having a stressfulimpact on the residents and visitors to Hawaii who are in manylocalities no longer able to experience “Quiet Hawaiian nights,” atleast without earplugs.

Example 8 Dried Pestiside Retains Killing Efficacy

When a sprayed ACS-P solution is left to dry on a surface, thepost-application composition remains lethal to frogs indefinitely anduntil the product is further diluted or washed away with water. If notkilled after coming into contact with this surface residue, frogs willvigorously seek to avoid further contact. One aspect of the lastinglethality of this composition is a product that is useful for formingbarriers in nurseries and commercial buildings.

Present manufacturing and distribution costs indicate ACS-P can be madeavailable at wholesale and retail costs that are substantially lowerthan citric acid. If desired, the product can be used to cut or extendcitric acid so as to double the quantity of solution while maintainingequal or lower cost than the original quantity. ACS-P is non-corrosiveand at the strengths used in this study, it has no significant hazardsto humans or animals.

Given the enormous buffering capacity of earth, there would benegligible risk of ground water contamination from the small amount ofpost-application runoff that would result from application as a mediumor mist spray. A drenching type application using a fire hose nozzle isnot required to use this product. The disadvantages of ACS-P are few.Normal eye and face mask protection as typically used in the applicationof any insecticide should be used when applying this product as minorirritation may occur if the product is allowed to come into contact withthe eyes, cuts, or wounds. This irritation would not be any moresubstantial than that caused by lemon juice and easily relieved byflooding the exposed area with water. Due to the acidity of theconcentrated form of this product, it will damage cotton clothing anddiscolor aluminum and galvanized metal, although still not corrosive tohuman skin. All in all, it is this author's opinion that this productrepresents a potentially valuable addition to the present array ofproducts available for combating the spread of Coqui frogs. More suchproducts are urgently needed and this product should be given strongsupport/consideration for EPA registration as a minimum risk pesticideto replace hydrated lime.

Example 9 Increasing Efficiency by Combining Acid and Salts

An object of the new pesticide product used to the control of Coquifrogs is a combination of different types of acids with otherorganic/inorganic acids and their respective salts. Previous exampleshave illustrated how various concentrations of Acidic Calcium Sulfate(ACS-100 or ACS-50) could be used as a low phytotoxic pesticide forCoqui frogs and other soft-bodied species. One of ordinary skill in theart will appreciate that the combinational use of other strong-, weak-and super-acids and salts can be formulated to remain toxic to frogs,but stay environmentally friendly according to EPA guidelines. As such,ACS-100, ACS-50, sulfuric acid, propionic acid, citric acid and/or theirrespective salts in combination with one or more of the previousmentioned acids is considered to be within the spirit and scope of theinvention.

As mentioned in other examples, ACS-P affords an advantage of havingcompositions capable of forming both a slurry and a dry product, whichcan be utilized in various types of applications. One disadvantage of anew composition (i.e. ACS-P, ACS-100, or ACS-50), which is unknown tothe environmental protection agency (“EPA”), is whether or not its usewould be approved quickly enough to stop frog infestations. As such, oneaspect of the current invention is to improve the frog killing effectsof compounds that are already listed as EPA approved pesticideingredients, or for frog eradication.

More specifically, compounds such as propionic acid, which are alreadyapproved as pesticides, can be used to take advantage of methodsdescribed herein to titrate lower pH levels for the purpose of killingfrogs, without being as toxic to plants. Propionic acid

(systematically named propanoic acid) is a naturally-occurringcarboxylic acid with chemical formula CH₃CH₂COOH. It is a clear liquidwith a pungent odor. The anion CH₃CH₂COO as well as the salts and estersof propionic acid are known as propionates (or propanoates) and areconsidered to be functional chemical equivalents thereof.

Although not wanting to be bound by current regulations and/or theory,ACS should be formulated to meet the HAZMAT cutoff of pH 2.0, however,titrating ACS with propionic acid or propionic acid salts can beutilized to increase or decrease the pH. In contrast, properlyformulated propionic acid is at least as effective as ACS alone inkilling frogs, and can be formulated will little effort to have a pHwithin the HAZMAT regulations of about 2.0. Unfortunately, an increasein concentration may lead to increased phytotoxicity. More specifically,propionic acid is available as a dry product and could be used in muchthe same way as citric acid is now being used and would cost less pergallon when compared to citric acid. For example, 1 gallon of 16% citricacid costs about $2.40/gallon (retail) and is considered phytotoxic tomany plants, whereas, 1 gallon of 16% propionic acid can be formulatedto have a lower pH and costs only about $1.00 per gallon with similar orsuperior phytotoxicity.

Although EPA regulations can present hurdles for entry of newcompositions into the pesticide market, citric acid and/or propionicacid are currently products that are on EPAs list 4 and can safely beused in pesticides without concern for non-target species and ornegative impact on the water table. As such, modified formulas of citricacid having lower phtotoxicity may also have a lower hurdle for EPAapproval. More specifically, it is possible to use ACS in a synergisticway with citric acid to actually lower the 16% concentration that isknow to have phytotoxic properties, while retaining the capacity to killthe frogs. For this reason, it may be advantageous to lower the 16%citric acid concentration in order to lower its known phytotoxiceffects.

Similarly, a composition of propionic acid is prepared as a liquid usingany of the following three methods shown below. The active ingredient isproprionic acid and either ACS or sulfurinc acid is used to adjust thepH downward or one of the propionic salts to adjust the pH upward. ACS-Pconsists of calcium sulfate saturated with sulfuric acid, can also beused to adjust the pH and/or to make slurry. ACS-P can be dried and/orinfused into bentonite clay, vermiculite, or some other functionalequivalent carrier capable of making a dry product. All formulations canbe made to vary in concentration according to the needs and applicationsof the user or EPA standards. For example, the pH of the final productsolution will for most purposes be at 2.0 or above in order to meet theHAZMAT criteria for non-hazardous products.

Formulation 1. Propionic Acid in Water.

To make an approximate 10% solution, add about 5-15 ml of propionic acid(90%+purity) to 100 ml of water. Mix and check pH to make sure it fallswithin the range from 2.0 to 2.5. If pH is greater than 2.5, titrate pHdownward by adding a small amount (0.25 to 1.0 ml) of sulfuric acid(90%+purity). If pH is less than 2.0 adjust pH upward using a smallamount (+/− about 0.5 to 1.0 gram) of sodium propionate. In a oneembodiment, the concentration range of propionic acid is in the range ofabout 5.0% to about 15%, and the pH is in the range of about 1.5 toabout 3.5. In a preferred embodiment, the concentration range ofpropionic acid is in the range of about 8.0% to about 12.5%, and the pHis in the range of about 1.8 to 2.8. In the most preferred embodiment,the concentration range of propionic acid is in the range of about 9.5%to about 10.5%, and the pH is in the range of about 2.2 to about 2.5.Alternatively, the pH can be titrated for the various concentrationranges using a superacid such as ACS-100, ACS-50, sulfuric acid,hydrochloric acid, or combination thereof (Note: a pipette or syringecan be used to slowly add sulfuric acid for adjusting pH downward tobetween about pH 2.0 and about pH 2.5. In some instances, it may beunadvisable to allow the total percentage of sulfuric acid used toadjust pH be above about 10% of the total solution, as not to surpassEPA tolerance limit for the use of sulfuric acid as a pH adjuster inpesticides. Additionally, propionic acid is a volatile chemical and mayevaporate out of solution within a given period of time. It is thereforeadvisable to use methods known in the art to prevent such evaporationfrom occurring. One having ordinary skill in the art will understandthat methods and ratios used to industrialize large scale manufacturingprotocols of these compositions is included in the spirit and scope ofthe invention.

Formulation 2. Salt of Propionic Acid in Water.

To make an approximate 10% solution, add about 10 grams of either sodiumor calcium propionate to about 100 ml of water, wherein sodiumpropionate is preferred because it does not leave a precipitant. Theinitial pH should be in the range of about 4.0 to 6.0. Adjust pH rangeto about 2.0-about 2.5 using sulfuric acid, ACS-P, ACS-100, or ACS-50.In a one embodiment, the concentration range of the salt of propionicacid is in the range of about 5.0% to about 15%, and the pH is in therange of about 1.5 to about 3.5. In a preferred embodiment, theconcentration range of the salt of propionic acid is in the range ofabout 8.0% to about 12.5%, and the pH is in the range of about 1.8 toabout 2.8. In the most preferred embodiment, the concentration range ofthe salt of propionic acid is in the range of about 9.5% to about 10.5%,and the pH is in the range of about 2.2 to about 2.5. Alternatively, thepH can be titrated for the various concentration ranges using asuperacid, ACS-100, ACS-50, sulfuric acid, or hydrochloric acid. Onehaving ordinary skill in the art will understand that methods and ratiosused to industrialize large scale manufacturing protocols of thesecompositions is included in the spirit and scope of the invention.

Formulation 3. ACS-P and ACS-100 in Water.

ACS-P and ACS 100 in water with or without the use of any otheringredients to adjust the pH of the solution, in one embodiment of thisinvention, an approximate 10% solution can be made by adding about 10grams of ACS-P 50 to 100 ml of tap water and mix thoroughly. The pHshould be should be in the range of about pH 1.1 to about pH 1.3. The pHcan be adjusted within the desired range of about pH 1.0 by adding a fewml of ACS. If the pH adjustment results in a pH that is below 1.0, asmall amount of calcium hydroxide can be added to increase the pH. Theclear liquid can be decanted from any precipitant; the decanted liquidcan be used as a spray. Save the white precipitant created in thisprocess for use as a slurry product as described in Formulation 4described below.

Since, the pH of this solution is about pH 1.0, it may harm certainplants by turning the leaves yellow, wherein most plants should recoverand plants should not die from application of this product. Although notwanting to be bound by theory, this product should be maintained in arange between about pH 0.5 to about pH 2.0. In a preferred embodiment,the pH range should be between about pH 0.9 and about pH 1.5. In themost preferred embodiment, the pH range should be about pH 1.0 to aboutpH 1.3 in order to remain effective at killing frogs. Additionally, tobe effective, about 1 ml of this product should come into direct contactwith the frog. Although not wanting to be bound by theory, more thanabout 1 ml of product may be needed to kill larger female frogs sincethey may withstand and may be capable of neutralizing the product due tofemales being more highly hydrated than male frogs. Although not wantingto be bound by theory, female frogs may retain more water in theirbodies in order to keep their eggs hydrated. One having ordinary skillin the art will understand that methods and ratios used to industrializelarge scale manufacturing protocols for these compositions is includedin the spirit and scope of the invention. (Note: By adding a stickerthat is normally used in pesticides to any of the above solutions in themanner known by one of ordinary skill in the art of sticker products,the efficacy of this pesticide product may be improved by the reductionin surface tension brought about as a result of adding the sticker.)

Formulation 4. ACS in Combination with Citric Acid.

Citric acid is currently the only substance approved by the HawaiiDepartment of Agriculture (HDOA) for use against Coqui frogs. Althoughnot wanting to be bound by theory, ACS can be used to extend andpotentiate citric acid and make a solution that is equally if not moreeffective at a cheaper price. In one embodiment, about 14 grams ofcitric acid can be added to about 10 ml ACS 100 or about 10 ml ofsulfuric acid or about 18 grams of ACS-P 50 and about 200 ml of water.The pH of this solution can be increased to about pH 2.0 by addingsodium propionate. In a preferred embodiment, the concentration range ofthe citric acid is in the range of about 5.0% to about 20%, and the pHis in the range of about 1.0 to about 3.0. In the most preferredembodiment, the concentration range of the salt of propionic acid is inthe range of about 9.5% to about 10.5%, and the pH is in the range ofabout pH 1.8 to about pH 2.2. Alternatively, the pH can be titrated forthe various concentration ranges using a superacid, ACS-100, ACS-50,sulfuric acid, or hydrochloric acid. One having ordinary skill in theart will understand that methods and ratios used to industrialize largescale manufacturing protocols of these compositions is included in thespirit and scope of the invention.

Formulation 5. The Product as Slurry.

The product as slurry may be useful for painting onto surfaces that aredesigned to serve as a barrier to the frogs, snails, nematodes, or othersoft-bodied invertebrates. Although not wanting to be bound by theory,these soft-bodied creatures will not cross a barrier containing theslurry and may be killed after contacting it. The slurry can besaturated into a piece of loosely woven cloth or painted on a flatsurface. Cloth saturated with slurry can be wrapped around a tree trunk,plant stem, or applied to a flat surface.

One simple way to make a slurry product is to reuse the precipitant fromFormulation 3 from above, or by adding a small amount of water to theACS-P sludge obtained from the Mionix ACS production factory. The finalpH of the slurry should be in the range of above zero and about pH 1.0.Although not wanting to be bound by theory, the precipitant fromFormulation 3 above will have a higher than desired pH, wherein a smallamount of ACS 100 or sulfuric acid will need to be added to lower the pHto the desired level. Although the solutions produced in Formulation 1,and Formulation 2 above can be made into slurry by adding about ten (10)to about twenty (20) grams of calcium carbonate, there may be no need todo this when ACS-P is readily available. One having ordinary skill inthe art will understand that methods and ratios used to industrializelarge scale manufacturing protocols of these compositions is included inthe spirit and scope of the invention.

Formulation 6. The Dry Product.

Drying the ACS-P and then processing the dried product to a desired sizeor by adding the liquid or slurry to a carrier such as a bentonite clay,vermiculite, lava cinder, or other inert suitable ingredient can make adry product. Although not wanting to be bound by theory, the adsorbed orabsorbed acids of this invention is believed to be available from theacidified clay as a residual pesticide capable of killing the frogs. Theclays or minerals suitable for this invention include montmorilloniteclay, phyllosilicate, Florisil®, bayerite, pseudoboehmite, alumina,silica gel, aluminum oxides, gibbisite, boehmite, and bauxite. Othercompounds capable of absorbing and releasing the acids are alsoconsidered to be within the spirit and scope of the invention. Similarto the slurry, the dry product has residual effects and can be used as abarrier for application to the surface soil of potted plants, around thebase of trees, or to make a perimeter defense zone in a nursery or otherarea that is protected from rain or irrigation water. The slurry productcan also be used in this same manner.

Although not wanting to be bound by theory, a dry product is made usingone of the liquid products above and adding about one (1) to two (2)parts of liquid solution to about four (4) parts carrier product, mix toform a thick slurry allow to dry. After drying process the dried productto the desired particle size and apply to the surface soil of pottedplants or spread around the area where a barrier to the frogs isdesired. In some instances, it may be appropriate to add a barrier toprevent the potted plant from the low pH product that could leach downinto the potting soil. Although not wanting to be bound by theory, ifthe low pH product leaches down into the soil as a result of it cominginto contact with irrigation water, the pH of the potting soil could bereduced to the point that it harms the plant, even if only temporarily.For example, one may use a piece plastic to cover the dry product soiland keep it separated from the potting soil. Namely, a piece of plasticin the range of about 3 mm to about 9 mm thick, however, one havingordinary skill in the art will understand that methods and ratios usedto utilize barriers made from functional equivalents of plastic forpreventing cross reactivity from these compositions and areas that needto be protected from these compositions, and are included in the spiritand scope of the invention.

Example 10 Frog Killing Time with Different Concentrations

The efficacy of a properly formulated solution of ACS-P fortified withACS 100 having a final pH of about pH 1.0, was found to have a similarkilling efficiency as hydrated lime. Additionally, this formulationkilled 10 out of 10 frogs within about 15 minutes. More over,concentrations using proprionic acid ranging from about 5% to about 10%were lethal to the frogs in the test group. It was found that the 10%solution of proprionic acid killed frogs faster than standard citricacid and the 5% proprionic acid killed equally fast, whereas the ACS-Palone took the longest time to kill the frogs.

Example 11 Composition and Method for Killing Frogs

One aspect of this invention is an acidic aqueous pesticide compositionfor killing a soft-bodied animal (e.g. a Coqui frog; a Coqui frog egg; atree frog, a cane toad, a slug, a nettle, a caterpillar, a nematode, anaphid, a spider mite, fruit fly larva, a varro mite and other softbodied insects that are usually regarded as pests, or a combinationthereof). The acidic aqueous pesticide composition comprises: an organicacid solution having concentration below 16% (w/v) as a percentage ofthe aqueous pesticide composition; and a pH for the acidic aqueouspesticide below pH 3.0, wherein, the organic acid is selected from: acitric acid, a propionic acid, or a mixture thereof. The acidic aqueouspesticide composition can be further defined as comprising an acidiccalcium sulfate (ACS) solution having a concentration below 20% (w/v) asa percentage of the aqueous pesticide composition. The acidic aqueouspesticide composition of can further be formulated to comprise asulfuric acid solution having a concentration below 10% (w/v) as apercentage of the aqueous pesticide composition. Additionally, theaqueous pesticide composition may further comprise a surfactant for thesurface area of the aqueous pesticide composition on the soft bodiedanimal of interest wherein the surfactant is selected from: an ionic-,anionic-, zwitterionic-surfactant, or combination thereof.

In a particular embodiment, the acidic aqueous pesticide compositioncomprises the organic acid concentration having a range of 5% to 15%(w/v); the ACS solution having a concentration of below about 20% (w/v);the sulfuric acid solution having a concentration about 0% (w/v); theacidic aqueous pesticide composition having a pH in the range of pH 0.8to pH 2.5. In a second particular embodiment, the acidic aqueouspesticide composition of claim 3, wherein, the organic acidconcentration having a range of 8% to 12% (w/v); the ACS solution havinga concentration of below 20% (w/v); the sulfuric acid solution having aconcentration about 0% (w/v); and the acidic aqueous pesticidecomposition having a pH in the range of pH 1.0 to pH 2.0. In a thirdparticular embodiment, the acidic aqueous pesticide composition of claim3, wherein, the organic acid concentration is about 12% (w/v); the ACSsolution having a concentration of about 20% (w/v); the sulfuric acidsolution having a concentration below 0% (w/v); and the acidic aqueouspesticide composition having a pH of about pH 1.5; and the soft-bodiedanimal is selected from: a Coqui frog; a Coqui frog egg. In a fourthparticular embodiment, the acidic aqueous pesticide compositioncomprises the organic acid concentration having a range of 5% to 15%(w/v); the ACS solution having a concentration of about 0% (w/v); thesulfuric acid solution having a concentration below about 10% (w/v); theacidic aqueous pesticide composition having a pH in the range of pH 0.8to pH 2.5. In a fifth particular embodiment, the acidic aqueouspesticide composition comprises the organic acid concentration having arange of 8% to 12% (w/v); the ACS solution having a concentration ofabout 0% (w/v); the sulfuric acid solution having a concentration belowabout 10% (w/v); and the acidic aqueous pesticide composition having apH in the range of pH 1.0 to pH 2.0. In a sixth particular embodiment,the acidic aqueous pesticide composition comprises the organic acidconcentration having about 12% (w/v); the ACS solution having aconcentration of about 0% (w/v); the sulfuric acid solution having aconcentration below 10% (w/v); and the acidic aqueous pesticidecomposition having a pH of about pH 1.5; and the soft-bodied animal isselected from: a mature Coqui frog; a Coqui frog egg; or a juvenileCoqui frog.

In an advantageous embodiment, a method of killing a soft-bodied animalof interest with an acidic pesticide composition is disclosed. Themethod comprising the steps of: Step 1: locating the soft-bodied animalor locating an area where the soft-bodied animal resides; Step 2:contacting the soft-bodied animal with the acidic pesticide composition;wherein, the acidic pesticide composition comprises: an acidic calciumsulfate (ACS) solution having a concentration of below about 20% (w/v);the acidic pesticide composition having a pH in the range of pH 0.8 topH 2.5; and the acidic pesticide composition is a liquid or a solidform; wherein, and the soft-bodied animal is selected from: a Coquifrog; a Coqui frog egg; a tree frog, a cane toad, a slug, a nettle, acaterpillar, a nematode, an aphid, a spider mite, fruit fly larva, avarro mite and other soft bodied insects that are usually regarded aspests, or a combination thereof.

In an advantageous embodiment, a method of killing a soft-bodied animalof interest with an acidic aqueous pesticide composition, the methodcomprising the steps of: Step 1: locating the soft-bodied animal orlocating an area where the soft-bodied animal resides; Step 1.1: placinga lure in the area inhabited by the soft-bodied animals of interest,wherein placing the lure occurs prior to the method step (1.2) ofspraying the acidic aqueous pesticide and the lure remains in the areaindefinitely; Step 1.2: spraying the acidic aqueous pesticidecomposition in the area inhabited by the soft bodied animals ofinterest, wherein, spraying the acidic aqueous pesticide compositionoccurs prior to the method step (2) of contacting the soft bodied animalof interest; Step 2: contacting the soft-bodied animal with the acidicaqueous pesticide composition; wherein, the acidic aqueous pesticidecomposition comprises: an organic acid solution having concentrationbelow 16% (w/v) as a percentage of the aqueous pesticide composition;and a pH for the acidic aqueous pesticide below pH 3.0; wherein, theorganic acid is selected from: a citric acid, a propionic acid, or amixture thereof; and the soft-bodied animal is selected from: a Coquifrog; a Coqui frog egg; a tree frog, a cane toad, a slug, a nettle, acaterpillar, a nematode, an aphid, a spider mite, fruit fly larva, avarro mite and other soft bodied insects that are usually regarded aspests, or a combination thereof; Step 3: waiting a period of time;wherein the period of time is in a range of 2 days to about 10 days.Step 3.1: checking the lure after the period of time; Step 3.2:discarding any Coqui frogs or Coqui frog eggs found in the lure. Step 4:repeating the method from step 1 until the area inhabited by thesoft-bodied animals has a significantly reduced number of soft-bodiedanimals of interest. The method of this invention uses a means forspraying the acidic aqueous pesticide composition in the area inhabitedby the soft bodied animals of interest is selected from: a hand sprayer;a garden sprayer with volumes less than about 10 liters; MountedSprayer-Semi Hydraulic; Trailed Sprayer; Mounted Sprayer With HydraulicBoom; Trailed Sprayer With High Wheel; Trailed Sprayer High Wheel WithElectronic Control Unit; Mounted Sprayer-Basic Type; MountedSprayer-Basic Type With Clean Water Tank; Garden Sprayer; High PressureDiaphragm Pump; Power Sprayer With Electric or Fuel Powered Engine;Fertilizer Spreader; Interrow Rotary Cultivator; or a functionalequivalent thereof. One of ordinary skill in the art will understandthere are many methods for spraying a liquid on a plant that are notlisted here, but are contained within the sprit and scope of thisinvention.

Example 12 Apparatus and Method for Killing Frogs on Plants

Although not wanting to be bound by theory, Now referring to FIG. 1 inthis application, a general pesticide recycling system for treatingplants of interest that are imported or exported from exotic locationshaving the potential for infestation with an invasive species 100. Thissystem is shown comprising an invasive species life cycle 110, a acidicpesticide recapture tank 120, a filter 125, an acidic acid transferand/or recycling pump. Typical fluid recycle lines are interconnectedamong the various components of the system with, for example, the inletside of the outlet transfer line 140 connected to the outlet of thetransfer or recycle pump 130. As the pesticide is pumped through thesprayer line 150 into the sprayer head 160, the pesticide istransitioned into droplets 170 that shower the plants of interest 180,which are sitting on acidic pesticide recapture tank 120. Not depictedin FIG. 1 but understood as comprising a part of the pesticide recyclingsystem, are power or air pressure lines supplying power to spray thepesticide onto the plants of interest.

In summary, the Coqui frog population has become a serious problem insome parts of the world. The previous methods for irradiating orcontrolling the frog population have been shown to be eitheruneconomical, restricted in scope or not environmentally friendly. Therelated art has shown that it is possible to impact frog populations ina limited capacity by utilizing physical means such as collection tubes;lures; and traps. In contrast, chemical methods of frog eradication haveshown better success than physical means (e.g. caffeine, pyrenone, andcitric acid solutions), however, these compounds may have a prolongedphytotoxic damage that impacts the entire ecosystem in heavily treatedareas. There is a need in the art for an expanded environmentally andphyoloycially friendly composition and methods of treating small andlarge areas of Coqui frog infestations.

This pesticide can be made or produced in a variety of wet and dryproducts and in varying concentrations. These include: 1) the dilutionof the active ingredient in its commercially available form with orwithout the use of other ingredients to adjust the final pH of thesolution. Possible active ingredients include but are not limited topropionic acid, lactic citric acid, lactic acid, and vinegar; 2) thedilution of the salts of the active ingredients listed in (1) in waterwith the addition of an acidulant to reactivate the active organic acidingredient and to adjust the final pH. Possible acidulants include butare not limited to acidic calcium sulfate, sulfuric acid, andhydrochloric acid; 3) the dilution of ACS 100 or it's by-product ACS-P50 in water with or without the use of any other ingredients to adjustthe pH of the solution; 4) preparation of slurry using any one of theproducts listed in 1-3 above. Additional inert ingredients such ascalcium carbonate or calcium hydroxide may be use to provide a calciumbase to increase the viscosity of the slurry; 5) combining any of theingredients as listed above with a sticker used in pesticides or otherinert carrier product such as a bentonite clay, vermiculite, lava cinderor other inert suitable ingredient to create a wet or dry product withresidual effects. The innovative use of highly diluted propionic acid asit commercially produced or is regenerated by using ACS or sulfuric acidin conjunction with sodium or calcium propionate produces a highlyeffective pesticide for the control of the Coqui frog and other invasivespecies named herein. It is not hazardous to humans or animals and isminimally phytotoxic. The EPA has no residual tolerance limitations forpropionic acid or its salts when used as active ingredients inpesticides, and approves up to a ten percent solution of sulfuric acidmay be added to pesticides to adjust pH. No harmful effects on theenvironment or birds and animals are anticipated from use of thispesticide. Ninety percent or above purity of propionic acid may be usedin water without a pH adjustor but is more corrosive than when used withACS-P 50 or ACS 100 as a pH adjustor. The solution strength recommendedherein has a minimum phytotoxicity for most plants (none if washed offwithin thirty minutes of application) and the added calcium (350 ppm)actually serves as a plant nutrient. As a highly diluted solution offood grade chemicals that are generally regarded as safe, this pesticidewill have negligible risk to humans, pets, farm animals, materialproducts such as sprayers, or the environment. ACS alone is used in thedrinking water of chickens and when combined with chlorine forms ahighly effective vegetable wash (These are previously patented uses byother entities). Once these two chemicals come into contact with theground the low pH (2.0-4.0) is quickly neutralized by the earth and/orsurface water or ground water leaving only calcium or calcium sulfate,both regarded as soil amendments. At present there are no other productsavailable that have comparable efficacy, safety, and cost-effectiveness.Due to the fact all the ingredients of this pesticide are GRAS andapprove for use in food, this inventor concludes that the new compoundformed by the combination of these substances should also be regarded asGRAS and therefore qualify as a minimum risk pesticide for the purposesdescribed herein. Approval by the EPA will be pursued under theprotection of the non-provisional patent to be issued under thisapplication.

REFERENCES CITED

The entire content of each of the following U.S. patent documents andpublished references are hereby incorporated by reference.

U.S. Patent Documents

-   1. U.S. Pat. No. 7,323,436 titled: “Adduct having an acidic solution    of sparingly-soluble group IIA complexes,” issued to Kemp et al., on    Jan. 29, 2008.-   2. U.S. Pat. No. 6,902,753 titled: “Acidic solution of    sparingly-soluble group IIA complexes,” issued to Kemp et al., on    Jun. 7, 2005.-   3. U.S. Pat. No. 6,881,424 titled: “Highly acidic metalated organic    acid,” issued to Kemp et al., on Apr. 19, 2005.-   4. U.S. Pat. No. 6,881,424 titled: “Highly acidic metalated organic    acid as a food additive,” issued to Kemp et al., on Oct. 26, 2004.-   5. U.S. Pat. No. 6,572,908 titled: “Highly acidic metalated organic    acid as a food additive,” issued to Kemp et al., on Jun. 3, 2003.-   6. U.S. Pat. No. 6,436,891 titled: “Adduct having an acidic solution    of sparingly-soluble group IIA complexes,” issued to Kemp et al., on    Aug. 20, 2002.-   Homeowner's guide to Stopping the spread of Coqui Frogs on Maui,    MAUI invasive Species Committee, Paia, Hi. May 2003.-   Product Safety Assessment Data Sheet of Propionic Acid, From Dow    Chemical, printed, 2008.-   MSDS for propionic Acid, From BASF.-   MSDS for ACS 50, from Mionix Corporation-   MSDS for ACS 100 from Mionix Corporation-   MSDS for Diluted ACS 50, from Mionix Corporation

What is claimed is:
 1. An acidic aqueous pesticide composition forkilling a soft-bodied animal, the composition comprising: (a) an organicacid solution having concentration in the range of about 5% to 15% (w/v)as a percentage of the aqueous pesticide composition; and (b) a pH forthe acidic aqueous pesticide below pH 3.0; wherein, the organic acid isselected from: a citric acid, a propionic acid, or a mixture thereof;and the soft-bodied animal is selected from: a Coqui frog; a Coqui frogegg; a tree frog, a cane toad, a slug, a nettle, a caterpillar, anematode, an aphid, a spider mite, fruit fly larva, a varro mite, or acombination thereof.
 2. The acidic aqueous pesticide composition ofclaim 1, further comprising: (c) an acidic calcium sulfate (ACS)solution having a concentration in a range of about 1% to 20% (w/v) as apercentage of the aqueous pesticide composition.
 3. The acidic aqueouspesticide composition of claim 2, further comprising: (d) a sulfuricacid solution having a concentration below in a range of about 1% to 10%(w/v) as a percentage of the aqueous pesticide composition.
 4. Theaqueous pesticide composition of claim 2, further comprising: (e) asurfactant for the surface area of the aqueous pesticide composition onthe soft bodied animal of interest wherein the surfactant is selectedfrom: an ionic-, anionic-, zwitterionic-surfactant, or combinationthereof.
 5. The acidic aqueous pesticide composition of claim 3,wherein, the organic acid concentration having a range of about 8% to12% (w/v); the ACS solution having a concentration of in the range ofabout 15% to 20% (w/v); and a surfactant, wherein the acidic aqueouspesticide composition having a pH in the range of pH 0.8 to pH 2.5. 6.The acidic aqueous pesticide composition of claim 3, wherein, theorganic acid concentration having a range of 8% to 12% (w/v); the ACSsolution having a concentration of about 5% to 15% (w/v); and the acidicaqueous pesticide composition having a pH in the range of pH 1.0 to pH2.5.
 7. The acidic aqueous pesticide composition of claim 3, wherein,the organic acid concentration is about 12% (w/v); the ACS solutionhaving a concentration of about 20% (w/v); the sulfuric acid solutionhaving a concentration below 0% (w/v); and the acidic aqueous pesticidecomposition having a pH of about pH 1.5; and the soft-bodied animal isselected from: a Coqui frog; a Coqui frog egg.
 8. The acidic aqueouspesticide composition of claim 3, wherein, the organic acidconcentration having a range of 5% to 15% (w/v); the ACS solution havinga concentration of about 0% (w/v); the sulfuric acid solution having aconcentration below about 10% (w/v); the acidic aqueous pesticidecomposition having a pH in the range of pH 0.8 to pH 2.5.
 9. The acidicaqueous pesticide composition of claim 3, wherein, the organic acidconcentration having a range of 8% to 12% (w/v); the ACS solution havinga concentration of about 0% (w/v); the sulfuric acid solution having aconcentration below about 10% (w/v); and the acidic aqueous pesticidecomposition having a pH in the range of pH 1.0 to pH 2.0.
 10. The acidicaqueous pesticide composition of claim 3, wherein, the organic acidconcentration is about 12% (w/v); the ACS solution having aconcentration of about 0% (w/v); the sulfuric acid solution having aconcentration below 10% (w/v); and the acidic aqueous pesticidecomposition having a pH of about pH 1.5; and the soft-bodied animal isselected from: a mature Coqui frog; a Coqui frog egg; or a juvenileCoqui frog.
 11. An acidic aqueous pesticide composition for killing asoft-bodied animal, the composition comprising: an acidic calciumsulfate (ACS) solution containing sparingly-soluble Group IIA complexes,prepared by mixing a mineral acid and a Group HA hydroxide, a Group IIAsalt of a dibasic acid, or a mixture of the Group IIA hydroxide andGroup HA salt followed by removing the solid formed; and diluting theACS solution concentration to a pH in the range of pH 0.8 to pH 2.5forming the acidic pesticide composition, wherein, and the soft-bodiedanimal is selected from: a Coqui frog; a Coqui frog egg; a tree frog, acane toad, a slug, a nettle, a caterpillar, a nematode, an aphid, aspider mite, fruit fly larva, a varro mite, or a combination thereof.12. The acidic aqueous pesticide composition of claim 11, furthercomprising: an organic acid solution having concentration range of 5% to20% (w/v) as a percentage of the aqueous pesticide composition, whereina pH for the acidic aqueous pesticide is below pH 3.0; the ACS has anacidic pH value and an acid normality value, wherein the ACS is lesscorrosive to a ferrous metal than is a solution of a mineral acid havingthe same acidic pH value as that of the ACS, and wherein the ACS is morebiocidal than a mixture of the organic acid and a metal salt of theorganic acid which mixture having the same acid normality value as thatof the ACS; and the organic acid is citric acid, propionic acid ormixture thereof.